TWI816948B - Polymer, resist composition containing the polymer, method of manufacturing a component using the resist composition, pattern forming method, and inversion pattern forming method - Google Patents

Abstract

Provided are a polymer, a resist composition containing the polymer, and a method of manufacturing a component using the resist composition, wherein the polymer is used in the electromagnetic field that passes through a particle beam or electromagnetic wave having high particle and photon energy. A resist composition that reduces the effects of sensitivity reduction and pattern roughness deterioration caused by reduction in energy application density in patterns formed by irradiation, has high absorption efficiency, and has excellent characteristics in sensitivity, resolution, and pattern performance.

In addition to the polarity conversion caused by the irradiation decomposition of particle beams or electromagnetic waves from ionic to non-ionic, at the same time, the polymer contains: an onium salt structural unit A that generates free radicals and acids and an acid-catalyzed bonding unit A Structure unit B.

The unit B is preferably a unit in which a compound represented by the following general formula (I) or (II) is bonded to an Sp group of the following formula (1) at an arbitrary position of the compound.

Description

Polymer, resist composition containing the polymer, method of manufacturing a component using the resist composition, pattern forming method, and inversion pattern forming method

Several aspects of the invention relate to polymers used in resist compositions. In addition, several aspects of the present invention relate to a resist composition containing the above-mentioned polymer, a method of manufacturing a component using the resist composition, a pattern forming method, and a method of forming an inversion pattern.

In recent years, photolithography technology has been actively used to manufacture display devices such as liquid crystal displays (LCDs) and organic EL displays (OLED) and to form semiconductor elements using photoresists. In the above-mentioned electronic components and electronic product packaging, i-rays with a wavelength of 365nm, h-rays (405nm) and g-rays (436nm) with longer wavelengths are widely used as active energy rays.

With the high integration of equipment, the requirements for miniaturization of photolithography technology are getting higher and higher. There are KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), extreme ultraviolet (EUV, wavelength There is a tendency for light with short wavelengths such as 13.5nm) and electron beam (EB) to be used for exposure. Photolithography technology using light with these short wavelengths, especially EUV or electron beams, enables single-pattern production. Therefore, resist compositions showing high sensitivity to EUV, electron beams, etc. will increasingly be needed in the future.

As the wavelength of the exposure light source becomes shorter, resist compositions are required to improve photolithographic characteristics so as to have high sensitivity to the exposure light source and resolution capable of reproducing fine-sized pattern formation. As a resist composition that satisfies such requirements, a chemically amplified resist using a photoacid generator is known (Patent Document 1).

However, in conventional chemically amplified resists, as the resolution line width of the resist becomes finer, it is difficult to fully suppress resist pattern collapse and decrease in line width roughness (LWR) of the line pattern. In order to suppress resist pattern collapse, it has been proposed to increase the cross-linking density of negative chemically amplified resists. However, defects such as bridges may occur due to swelling during development. Although it is necessary to prevent resist pattern collapse and bridge formation, chemically amplified resist compositions used in conventional EUV or electron beams have been limited due to small absorption of EUV or electron beams and a small amount of acid included in the resist. It is very difficult to increase the cross-linking density with high sensitivity while maintaining the resolution and patterning performance due to the diffusion of acid generated by the generator.

[Existing technical documents]

【Patent Document】

Patent Document 1: Japanese Patent Application Laid-Open No. 9-90637

An object of several aspects of the present invention is to provide a polymer for a resist composition that can significantly suppress acid diffusion and has excellent resolution and pattern characteristics. The polymer utilizes particles in addition to In addition to the acid generated from the acid generator by irradiation of electron beams or electromagnetic waves, particularly electron beams, EUV, etc., reactions caused by irradiation of electron beams, EUV, etc., which occur simultaneously with the acid catalytic reaction, are directly utilized.

An object of some aspects of the present invention is to provide a resist composition containing the above-mentioned polymer, a manufacturing method of a component using the resist composition, a pattern forming method, and an inversion pattern forming method.

The inventors of the present invention conducted intensive research to solve the above-mentioned problems and found that high sensitivity can be achieved by using a polymer containing unit A having an onium salt structure and unit B having a specific structure as a polymer of a resist composition. degree and can suppress line width roughness (LWR), thereby completing several aspects of the present invention.

More specifically, the following conclusions were obtained by irradiating a resist composition containing the above polymer with a particle beam or an electromagnetic wave. First, the above-mentioned unit A decomposes to cause a large polarity conversion from ionic to nonionic. At the same time, the acid generated by the decomposition of the unit A causes an intramolecular cross-linking reaction between the units B or between units B and units different from the unit B. Therefore, a resist composition containing the above polymer can suppress acid diffusion, have high sensitivity, and can suppress line width roughness (LWR).

One aspect of the present invention that solves the above problems is a polymer including unit A having an onium salt structure and generating a first radical by irradiation with a particle beam or electromagnetic wave, and unit B having an acid Catalytic reaction bonding structures.

The above unit B is preferably a compound represented by the following general formula (I) or (II) at any position of the compound A unit bonded to the Sp group of the following formula (1).

(In the above general formula (I),

R ² and R ³ are each independently selected from any one of the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group,

n ¹ is an integer of 0 or 1,

n ⁴ and n ⁵ are integers from 1 to 2 respectively, n ⁴ +n ⁵ is 2 to 4,

When n ⁴ is 1, n2 is an integer from 0 to 4. When n ⁴ is 2, n ² is an integer from 0 to 6.

When n ⁵ is 1, n3 is an integer from 0 to 4. When n ⁵ is 2, n ³ is an integer from 0 to 6.

When n ² is 2 or more and R ² is an electron donating group or an electron withdrawing group, the two R ² can be selected from oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups directly or through a single bond. Any one of the formed groups forms a ring structure with each other,

When n ³ is 2 or more and R ³ is an electron-donating group or an electron-withdrawing group, the two R ^3s may be selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group directly or via a single bond. Each of the formed groups forms a ring structure with each other.

In the above general formula (II),

R ⁴ is each independently selected from any one of the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group,

At least one of R ⁴ is the above-mentioned electron donating group,

^R5 is any one selected from the group consisting of an alkyl group that may have a hydrogen atom; a substituent; and an alkenyl group that may have a substituent, and at least one methylene group in the above R5 may be substituted by a divalent heteroatom-containing group,

n ⁶ is an integer from 0 to 7,

n ⁷ is 1 or 2, when n ⁷ is 1, n ⁶ is an integer from 0 to 5, when n ⁷ is 2, n ⁶ is an integer from 0 to 7,

When n ⁶ is 2 or more and R ⁴ is an electron donating group or an electron withdrawing group, the two R ^4s may be selected from oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups directly or through a single bond. Each of the formed groups forms a ring structure with each other. )

(In the above formula (1),

L is selected from carbonyloxy, carbonylamino, phenylenediyl, naphthalenediyl, phenylenedioxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl and Any one of the group consisting of naphthalenedioxycarbonyl,

Sp is a straight-chain, branched or cyclic alkylene group with 1 to 6 carbon atoms that may have direct bonding; a substituent; and a straight-chain, branched or cyclic alkylene group with 1 carbon atom that may have a substituent. Any one of ~6 alkenylene groups, at least one methylene group in Sp can be substituted by a divalent heteroatom-containing group,

R ¹ is selected from the group consisting of a hydrogen atom; a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group with 1 to 6 carbon atoms. Any of the above-mentioned alkyl groups and alkenyl groups in R ¹ may have at least one hydrogen atom substituted by a substituent,

* represents the bonding site with the compound represented by the general formula (I) or (II). )

One aspect of the present invention is a resist composition containing the above polymer.

In addition, one aspect of the present invention is a method for manufacturing a component, which includes the following steps: forming a resist film on a substrate using the above resist composition; and exposing the resist using a particle beam or an electromagnetic beam. a photolithography step of etching the film; and a patterning step of developing a photolithography resist pattern on the exposed resist film.

One aspect of the present invention is a pattern forming method, which includes the following steps: forming a resist film on a substrate using the resist composition; and exposing the resist film using a particle beam or an electromagnetic beam. a photolithographic step; and a patterning step of developing a photolithographic resist pattern on the exposed resist film.

One aspect of the present invention is a method for forming an inversion pattern, which includes the following steps: a resist film forming step of forming a resist film on a substrate using the above resist composition; using a particle beam or an electromagnetic beam to expose the above A photolithography step of a resist film; a pattern forming step of developing a photoresist pattern on the exposed resist film; and etching by coating a reversal pattern composition to cover at least a portion of the photoresist pattern. The step of removing the resist film from the above-mentioned exposed resist pattern surface portion to obtain a reverse pattern.

When the polymer according to some aspects of the present invention is used as a resist composition, in addition to the polarity conversion caused by the dispersion changing from ionic to nonionic due to irradiation of particle beams, electromagnetic waves, etc., it also produces Acids and free radicals. Thus, by simultaneously utilizing two reactions that perform cross-linking reactions within the molecules of the polymer, patterns can be formed even if acid diffusion is suppressed, so the characteristics of sensitivity, resolution, and pattern performance are excellent.

FIG. 1 shows SEM images of patterns obtained in Examples 8 to 10.

FIG. 2 shows SEM images of patterns obtained in Example 9 and Comparative Example 3.

Figure 3 illustrates pattern formation using a resist composition of one aspect of the present invention.

Figure 4 illustrates pattern formation using a resist composition of one aspect of the present invention.

Figure 5 illustrates pattern formation using a resist composition of one aspect of the present invention.

In the present invention, "particle beam or electromagnetic wave" refers to not only electron beams and extreme ultraviolet rays but also ultraviolet rays and the like, but is preferably electron beams or extreme ultraviolet rays.

In the present invention, "irradiation by particle beam or electromagnetic wave" means that at least part of the polymer is irradiated with particle beam or electromagnetic wave. Active species are generated by irradiating a localized portion of the polymer with a particle beam or electromagnetic wave to excite or ionize a specific portion of the polymer. The active species decomposes part of the above-mentioned unit, or the active species is attached to the above-mentioned unit, or the active species causes the dehydration of the hydrogen element of the above-mentioned unit. Secondary reactions such as ionization produce free radicals or acids. Here, "active species" refers to radical cations, radicals, electrons, etc.

The present invention will be described in detail below, but the present invention is not limited thereto.

<1>Polymer

A polymer according to some aspects of the present invention is a polymer including unit A having an onium salt structure that generates a first radical, and unit B having a structure bonded by an acid-catalyzed reaction. The unit B is not particularly limited as long as it has a structure in which two molecules are bonded by an acid-catalyzed reaction, but preferably, for example, a compound represented by the above general formula (I) or (II) at any position of the compound and A unit to which the Sp group of the above formula (1) is bonded.

By irradiating at least part of the polymer containing the unit A and the unit B with a particle beam or an electromagnetic wave, anions and first radicals are generated from the unit A by reduction of the unit A. The anion produced becomes an acid by bonding with a proton.

It is obtained by using an acid as a catalyst to react the above-mentioned units B with each other or the above-mentioned units B with other units having a hydroxyl group to cause etherification and a cross-linking reaction.

The first radicals generated from the units A form a bond with each other or with the second radicals generated when the polymer contains a unit that generates radicals and the first radicals, and the units A form a bond with each other. Or it is obtained by causing an intramolecular cross-linking reaction between the above-mentioned unit A and a unit that generates radicals (for example, unit C to be described later).

(Unit A)

The unit A is not particularly limited as long as it has an onium salt structure and is polarized by irradiating at least part of the polymer with a particle beam or electromagnetic wave, that is, generating anions and radicals by reduction of the onium salt. Specific examples include those represented by the following formula (I).

In the present invention, "polarity conversion" refers to directly or indirectly changing the polarity from ionic to nonionic through irradiation of particle beams or electromagnetic waves.

In the above general formula (III), M ⁺ is a sulfonium ion or an iodide ion, and X ^- is a monovalent anion.

L is not particularly limited as long as it can bond the main chain constituting the polymer to the above-mentioned onium salt structure. For example, L is selected from the group consisting of carbonyloxy group, carbonylamino group, phenylenediyl group, naphthalenediyl group, and phenylenedioxy group. Any one of the group consisting of naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyloxy, phenylenedioxycarbonyl and naphthalenedioxycarbonyl.

From the viewpoint of ease of synthesis, L is preferably a carbonyloxy group or the like.

Sp is not particularly limited as long as it can serve as a spacer between the above-mentioned L and the above-mentioned onium salt. For example, it can be a direct bond; it can have a linear, branched or cyclic number of carbon atoms with a substituent. Alkylene group of 1 to 6; and the number of straight chain, branched or cyclic carbon atoms that may have substituents Any of the alkenylene groups of 1 to 6, at least one methylene group in the above-mentioned Sp may be substituted by a divalent heteroatom-containing group.

Examples of the linear alkylene group having 1 to 6 carbon atoms in Sp include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and the like.

Examples of the branched alkylene group having 1 to 6 carbon atoms in Sp include isopropylene group, isobutylene group, tert-butylene group, isopentylene group, tert-pentylene group, 2-ethylhexenyl group, etc. .

Examples of the cyclic alkylene group having 1 to 6 carbon atoms in Sp include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and the like.

At least one methylene group in Sp may be substituted by a divalent heteroatom-containing group. Examples of divalent heteroatoms include -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, and -NH-CO-O-. , -O-CO-NH-, -NH-, -N(R ^Sp )-, -N(Ar ^Sp )-, -S-, -SO- and SO ₂ -. Examples of RSp include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Examples of ArSp include phenyl and naphthyl groups having 12 or less carbon atoms, and examples include aryl groups. In addition, the number of carbon atoms of the alkylene group of Sp mentioned above does not include the number of carbon atoms of the substituent which Sp may have.

Examples of substituents that Sp may have (hereinafter referred to as "first substituents") include: halogen atoms such as fluorine atom, chlorine atom, bromine atom or iodine atom; hydroxyl group; linear or cyclic carbon atoms with 1 to 12 alkyl group; instead of at least one methylene group of the alkyl group, the skeleton includes a group selected from -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, -NH-, -N(R ^Sp )-, -N(Ar ^Sp )-, -S-, -SO-, and SO ₂ ^- A heteroatom-containing group consisting of alkyl; aryl; and heteroaryl, etc.

Examples of the alkyl group containing the first substituent of Sp in the skeleton and the alkyl group containing a heteroatom group include an alkyl group in which the alkylene group of Sp is a monovalent group.

Examples of the aryl group as the first substituent of Sp include the same options as those for Ar ^Sp described above.

Examples of the heteroaryl group as the first substituent of Sp include groups having a skeleton such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, and pyrazine.

Sp may be directly bonded, but from the viewpoint of radical rebonding between units A and cross-linking reaction between units B, a pad structure in which molecules are easily movable is preferred. Preferred examples include an alkylene group, an alkyleneoxy group, an alkylenecarbonyloxy group, and the like.

R ¹ is selected from the group consisting of a hydrogen atom; a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group with 1 to 6 carbon atoms. In any one of the groups, at least one hydrogen atom in the above-mentioned alkyl group and alkenyl group in R ¹ may be substituted by a substituent. The substituents that R ¹ may have include the same options as the above-described first substituent.

Examples of the linear alkyl group having 1 to 6 carbon atoms in R ¹ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and the like.

Examples of the branched alkyl group having 1 to 6 carbon atoms in R ¹ include isopropyl, isobutyl, tert-butyl, isopentyl, tert-amyl, 2-ethylhexyl, and the like.

Examples of the cyclic alkyl group having 1 to 6 carbon atoms in R ¹ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

Examples of the linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms for R ¹ include at least one of the carbon-carbon single bonds of the linear alkyl group, branched alkyl group and cyclic alkyl group shown above. One substituted by a carbon-carbon double bond.

In addition, in the alkyl group and alkenyl group of R ¹ , at least one hydrogen atom may be substituted by a fluorine atom, which is a fluorinated alkyl group and a fluorinated alkenyl group. All hydrogen atoms may be substituted by the above-mentioned first substituent. The fluorinated alkyl group is preferably trifluoromethyl or the like.

As the unit A, preferably, in the above formula (III), R ¹ is a hydrogen atom or a linear alkyl group, and L is a carbonyloxy group, a carbonylamino group, or a phenylene diyl group.

In addition, from the viewpoint of LWR, it is preferable that the above-mentioned unit A has L as a carbonyloxy group or a carbonylamino group, Sp as a direct bond, and ^R1 as a methyl group, and the methyl group has 1 to 4 carbon atoms in the above-mentioned first substituent. A unit of at least one of an alkyl group, a halogen atom and an aryl group. ^R1 having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

Examples of M ⁺ include sulfide cations and iodine cations having a bonding hand bonded to Sp, and are specifically represented by the following general formulas (a1) and (a2).

【Chemical 4】

In the above general formula, R ^6a is an alkylene group with 1 to 6 carbon atoms selected from linear, branched or cyclic carbon atoms that may have substituents; linear, branched or cyclic carbon atoms that may have substituents. Alkenylene group with 1 to 6 atoms; arylene group with 6 to 14 carbon atoms that may have a substituent; heteroarylene group with 4 to 12 carbon atoms that may have a substituent; and a group consisting of direct bonding any of the groups.

Examples of the linear, branched or cyclic alkylene group of R ^6a include the same options as the alkylene group of Sp mentioned above.

Examples of the linear, branched or cyclic alkenylene group of R ^6a include the same options as the alkenylene group of Sp mentioned above.

Examples of the arylene group having 6 to 14 carbon atoms in R ^6a include phenylene group, naphthylene group, and the like.

Examples of the heteroarylene group having 4 to 12 carbon atoms in R ^6a include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, indole, purine, quinoline, isoquinoline, and chromene. Divalent radicals of skeletons such as thianthrene, dibenzothiophene, phenothiazine, phenoxazine, xanthenes, acridine, phenazine and carbazole, etc.

Examples of the alkyl group, alkenyl group, aryl group and heteroaryl group of R ^6b include the above-mentioned alkylene group, alkenylene group, arylene group and heteroarylene group of R ^6a , which are monovalent.

Examples of the substituents of R ^6a and R ^6b include the same substituents as the first substituent that the above-mentioned Sp may have.

In the above formula (a1), any two of R ^6a and two R ^6b may be directly or via a single bond selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group. Either, forms a ring structure with these bonded sulfur atoms.

Examples of the divalent nitrogen atom-containing group include those containing a nitrogen atom among the divalent heteroatom-containing groups. Specific examples include -NHCO-, -CONH-, -NH-CO-O-, and -O-CO-NH-. , -NH-, -N(R ^Sp )- and N(Ar ^Sp )-, etc.

Examples of the sulfide cation of M ⁺ include those having a structure shown below and having a bonding hand bonded to the above-mentioned Sp at an arbitrary position. In addition, the compound shown below may have the said substituent at the position corresponding to the said ^R6a and ^R6b .

【Chemical 5】

X ^- is selected from alkyl sulfate anion, aryl sulfate anion, alkyl sulfonate anion, aryl sulfonate anion, alkyl carboxylate anion, aryl carboxylate anion, tetrafluoroborate anion , hexafluorophosphonate anion, dialkyl sulfonimide anion, trialkyl methyl sulfonate anion, tetraphenylborate anion, hexafluoroantimonate, monovalent metal onium anion and hydrogen acid containing these Any one of the group of anions. In addition, at least one of the hydrogen atoms of the alkyl group and the aryl group in ^X- may be substituted with a fluorine atom.

Examples of metal onium anions include NiO ₂ ^- , SbO ₃ ^- , and the like. In addition, VO ₄ ^3- , SeO ₃ ^2- , SeO ₄ ^2- _, MoO ₄ ^2- , SnO ₃ ^{2- , TeO 3 2-} , TeO ₄ ^2- , TaO ₃ ^2- , WO ₄ ^{2- ,} etc. can also be used. The divalent to trivalent anions are appropriately added with H ⁺ , sulfonium ions, iodide ions, monovalent to divalent metal cations, etc. to become monovalent anions. The above-mentioned monovalent to divalent metal cations may be general cations, and examples thereof include Na ⁺ , Sn ²⁺ , Ni ²⁺ and the like.

In addition, when X ^- is a metal onium anion, the metal is preferably selected from the group consisting of Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, At least one of the group consisting of Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra. The reason is that the sensitivity to particle beams or electromagnetic waves is increased. Preferable examples of the metal onium anion include SbF ₆ ^- , SbO ₃ ^- , Sb(OH) ₆ ^- , HWO ₄ ^-, and the like.

The unit A is preferably a unit represented by the following formula (IV).

In the above- ^mentioned general formula (IV), L, Sp ^{and X-} are respectively the same as L, ^{Sp and 6b} .

The anion of the unit A is preferably an anion with high hydrophilicity from the viewpoint of improving contrast during photoresist pattern formation. Specifically, alkyl sulfate anions, aryl sulfate anions, alkyl sulfonate anions, aryl sulfonate anions, alkyl carboxylate anions, Aryl carboxylate anions, etc.

One aspect of the present invention may have two or more types of the above-mentioned unit A in the above-mentioned polymer. For example, it is preferable to use one photoacid generator unit A and the other photodecomposable alkali unit A. It is preferable to use the photodecomposable alkali unit A whose acid strength is weaker than that of the photoacid generator unit A in combination with the photoacid generator unit A.

In addition, when the above-mentioned polymer has two or more types of the above-mentioned units A, units having the same M ⁺ X ^- moiety and different substituents such as R ¹ or L can be used.

(Unit B)

A compound in which at least one of the compounds represented by the following general formula (I) or (II) is bonded to the * part of the following formula (1) at an arbitrary position of the compound is included in the polymer as unit B. When the above-mentioned polymer contains the above-mentioned unit B, the sensitivity to particle beams or electromagnetic waves can be improved.

In the above general formula (I), R ² and R ³ are each independently selected from any one of the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group. If at least one of R ² and R ³ is the above-mentioned electron donating group, acid reactivity can be improved, which is preferable.

E is preferably selected from any one of the group consisting of direct bonding; oxygen atom; sulfur atom; and methylene group.

n ¹ is an integer of 0 or 1, n ⁴ and n ⁵ are integers of 1 to 2 respectively, and n ⁴ + n ⁵ is 2 to 4.

When n ⁴ is 1, n ² is an integer from 0 to 4, and when n ⁴ is 2, n ² is an integer from 0 to 6.

When n ⁵ is 1, n ³ is an integer from 0 to 4, and when n ⁵ is 2, n ³ is an integer from 0 to 6.

When n ² is 2 or more and R ² is an electron donating group or an electron withdrawing group, the two R ² can be selected from oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups directly or through a single bond. Each of the formed groups forms a ring structure with each other.

When n ³ is 2 or more and R ³ is an electron-donating group or an electron-withdrawing group, the two R ^3s may be selected from an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group directly or via a single bond. Each of the formed groups forms a ring structure with each other.

Examples of the divalent nitrogen atom-containing group used to form a ring structure in the above formula (I) are the same as the divalent nitrogen atom-containing group in the above formula (a1).

In the above general formula (II), R ⁴ is each independently selected from the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group. Preferably, at least one of R ⁴ is the electron donating group, thereby improving acid reactivity.

R ⁵ is any one selected from the group consisting of an alkyl group which may have a hydrogen atom; a substituent; and an alkenyl group which may have a substituent. At least one methylene group in the above R ⁵ may be substituted by a divalent heteroatom-containing group.

Examples of the alkyl group for R ⁵ include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Specific examples include the same alkyl groups as R ^6b .

Examples of the substituent that R ⁵ has include the same substituents that the above-mentioned Sp has as the above-mentioned first substituent.

n ⁶ is an integer from 0 to 7,

n ⁷ is 1 or 2, when n ⁷ is 1, n ⁶ is an integer from 0 to 5, and when n ⁷ is 2, n ⁶ is an integer from 0 to 7.

When n ⁶ is 2 or more and R ⁴ is an electron donating group or an electron withdrawing group, the two R ^4s may be selected from oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups directly or through a single bond. Each of the formed groups forms a ring structure with each other. )

Examples of the divalent nitrogen atom-containing group forming a ring structure in the above formula (II) are the same as the divalent nitrogen atom-containing group in the above formula (a1).

In the above formula (1), R ¹ , L and Sp are the same as in the above general formula (III).

Examples of the electron-donating groups of R ² , R ³ and R ⁴ include: alkyl (-R ¹³ ), and alkenyl in which at least one of the carbon-carbon single bonds of the alkyl group (-R ¹³ ) is replaced by a carbon-carbon double bond; In addition, for the aromatic ring to which the methine carbon of the hydroxyl group is bonded, an alkoxy group (-OR ¹³ ), an alkylthio group (-SR ¹³ ), etc. are bonded to the ortho- or para-position of the aromatic ring.

The above-mentioned R ¹³ is preferably an alkyl group having 1 or more carbon atoms. Specific examples of the alkyl group having 1 or more carbon atoms include preferably linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. Base; isopropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, 2-ethylhexyl and other branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, diamond Alicyclic alkyl groups such as alkyl-1-yl, adamantan-2-yl, norbornan-1-yl and norbornan-2-yl; one of the hydrogens in these is composed of trimethylsilyl, triethyl A silyl-substituted alkyl group substituted by a trialkylsilyl group such as a silyl group and a dimethylethylsilyl group; none of the above alkyl groups is directly bonded to the aromatic aromatic property of the above compound (I) or (II) An alkyl group in which at least one of the hydrogen atoms contained in the carbon atoms of the ring is substituted with a cyano group, a fluoro group, or the like. The above-mentioned R ¹³ preferably has 4 or less carbon atoms.

Examples of the electron-withdrawing groups of R ² , R ³ and R ⁴ include: -C(=O)R ^13a (R ^13a is a linear, branched or cyclic carbon atom number of 1 to 12 which may have a substituent) Alkyl group.); -C(=O)R ^13b (R ^13b is an aryl group with 6 to 14 carbon atoms that may have a substituent.); -C(=O)OR ^13a ; -SO ₂ R ^13a ; - SO ₂ R ^13b ; nitro; -OR ^13a substituted in the meta position of nitroso, trifluoromethyl, and hydroxyl; -OR ^13b substituted in the meta position of hydroxyl; -SR ^13a substituted in the meta position of hydroxyl; -SR ^13b substituted at the meta position of the hydroxyl group; and at least one of the carbon-carbon single bonds in -C(=O)R ^13a , -C(=O)OR ^13a , -SO ₂ R ^13a and SR ^13a is composed of carbon A group substituted by a carbon double bond or a group substituted by a carbon-carbon triple bond.

Examples of substituents that R ^13a and R ^13b may have include the same options as the first substituent that Sp has.

Specific examples of the compound represented by the general formula (I) or (II) include the compounds shown below.

【Chemical 9】

One aspect of the polymer of the present invention contains any one of the compounds represented by the general formula (I) or (II) as the unit B bonded to the * part of the above formula (1) at an arbitrary position of the compound. in polymers. In this case, the position bonded to the * part of the above formula (1) is preferably any one of R ² , R ³ and R ⁴ . For example, in the case of a compound represented by the above general formula (I), it is preferable to have a bonding hand bonded to the * part of the above formula (1) instead of one H in R ² .

The unit B preferably includes a unit in which R ¹ in the above formula (1) is a hydrogen atom, a linear alkyl group, an L carbonyloxy group, a carbonylamino group, or a phenylene diyl group.

In addition, from the viewpoint of LWR, the above-mentioned unit B preferably has L being a carbonyloxy group or a carbonylamino group, Sp being a direct bond, R ¹ being a methyl group, and the methyl group having 1 to 4 carbon atoms in the above-mentioned first substituent. At least one unit of an alkyl group, a halogen atom and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

In one aspect of the present invention, the polymer may contain two or more types of units B.

(Unit C)

The above-mentioned unit C is a unit having a free radical generating structure, and the free radical generating structure contains at least one multiple bond selected from the group consisting of multiple bonding of carbon atoms and multiple bonding of carbon atoms and multiple bonding of carbon atoms and heteroatoms, There is no particular limitation as long as at least a part of the polymer is irradiated with a particle beam or an electromagnetic wave to generate a second radical.

An intramolecular cross-linking reaction can be caused between the unit A and the unit C by irradiating a particle beam, an electromagnetic wave, or the like.

The multiple bonding in unit C is not particularly limited as long as it can generate radical cations due to the influence of particle beams or electromagnetic waves, and the radical cations decompose into second radicals and cations, but it is not included in benzene aromatics. And it is preferably at least any one of the bonds shown below. Benzene aromatics include, in addition to benzene, aromatics having benzene skeletons such as naphthalene and azulene. "Multiple bonds not included in benzene aromatics" means multiple bonds not included in these aromatics.

【Chemical 10】

Specifically, the radical-generating structure containing the multiple bonding has any one unit selected from the group consisting of an alkylphenone skeleton, a acyl oxime skeleton, and a benzyl ketal. Having these skeletons may have any substituent, and the unit having an alkylbenzophenone skeleton includes an α-aminoacetophenone skeleton and the like. More specifically, a structure represented by at least one of the following general formulas (V) to (VII) is preferred.

In the above-mentioned general formulas (V) to (VII), R ¹ , L, and Sp are respectively selected from the same options as L and Sp of the above-mentioned general formula (III).

R ⁷ is each independently selected from a hydrogen atom; a hydroxyl group; -R ^a (R ^a is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms that may have a substituent); -OR ^a ; and At least one of the carbon-carbon single bonds in R ^a is substituted by a carbon-carbon double bond; and -R ^b (R ^b is an aryl group with 6 to 14 carbon atoms that may have a substituent). One or two or more R ³ can form a ring structure through a single bond directly or through any one selected from the group consisting of oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups.

Examples of R ^a include the same options as the alkyl group of R ^13a . Examples of R ^b include the same options as the aryl group of R ^13b .

Examples of substituents that R ^a and R ^b may have include the same substituents as the substituents Sp has above.

However, three of R ⁷ in the above formula (V) are preferably non-hydrogen atoms. In addition, in the above formula (V), at least one of three R ⁷ is preferably OH. By having OH as the above-mentioned unit C, a cross-linking reaction between unit B and unit C can be caused.

R ⁸ is selected from -R ^a ; -R ^b ; -OR ^a ; -SR ^a ; -OR ^b ; -SR ^b ; -OC(=O)R ^a ; -OC(=O)R ^b ; -C( =O)OR ^a ;-C(=O)OR ^b ;-OC(=O)OR ^a ;-OC(=O)OR ^b ;-NHC(=O)Ra;-NR ^a C(=O)R ^a ;-NHC(=O)R ^b ;-NR ^b C(=O)R ^b ;-NR ^a C(=O)R ^b ;-NR ^b C(=O)R ^a ;-N(R ^a ) ₂ ;-N(R ^b ) ₂ ;-N(R ^a )(R ^b );-SO ₃ R ^a ;-SO ₃ Rb;-SO ₂ R ^a ;-SO ₂ R ^b ;The carbon in -R ^a Any one of the group consisting of at least one carbon single bond substituted by a carbon-carbon double bond; and a nitro group.

In the above formula (V), when m ¹ is 2 or more, the two R ⁸ may be any one selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group and a methylene group, directly or through a single bond. a ring structure

m ² is an integer from 1 to 3. When m ² is 1, m ¹ is an integer from 0 to 4. When m ² is 2, m ¹ is an integer from 0 to 6. When m ² is 3, m ¹ is an integer from 0 to 8. .

R ⁹ is selected from linear, branched or cyclic alkylene groups with 1 to 12 carbon atoms that may have substituents; linear, branched or cyclic alkylene groups with 1 to 12 carbon atoms that may have substituents. Alkyleneoxy group; a straight-chain, branched or cyclic alkenylene group with 1 to 12 carbon atoms that may have a substituent; a straight-chain, branched or cyclic alkenylene group with 1 carbon atom that may have a substituent Any one of the group consisting of an alkenyleneoxy group with ~12 carbon atoms; an arylene group with 6 to 14 carbon atoms that may have a substituent; and a heteroarylene group with 4 to 12 carbon atoms that may have a substituent.

Examples of the substituent that R ⁹ may have include the same options as the first substituent that Sp has.

Specific examples of the unit C include those shown below.

The unit C is preferably a unit in which R ¹ is a hydrogen atom or a linear alkyl group, and L is a carbonyloxy group, a carbonylamino group or a phenylenediyl group in the above formulas (V) to (VII).

In addition, from the viewpoint of LWR, the above-mentioned unit C preferably has L being a carbonyloxy group or a carbonylamino group, Sp being a direct bond, R ¹ being a methyl group, and the methyl group having 1 to 4 carbon atoms in the above-mentioned first substituent. At least one unit of an alkyl group, a halogen atom and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

One aspect of the present invention may have two or more types of the above-mentioned units C in the above-mentioned polymer.

(Unit D)

One type of polymer of the present invention preferably contains a unit having an aryloxy group (hereinafter referred to as "unit D") in addition to the above-mentioned units A to C. The unit D preferably has a phenol structure bonded to the * part of the above formula (1) at any position of the structure.

The unit D is not particularly limited as long as it can improve the acid production efficiency of the unit A. Specific examples thereof include units shown below.

Preferably, R ¹¹ in the above general formula is each independently selected from the group consisting of a hydrogen atom and an alkyl group. The alkyl group of R ¹¹ may have a substituent.

Examples of the above-mentioned alkyl groups include linear or branched ones having 1 to 5 carbon atoms, such as methyl, ethyl, isopropyl, n-isopropyl, sec-butyl, tert-butyl, n-butyl, and pentyl. of alkyl.

Examples of substituents that the alkyl group may have include hydroxyl, sulfonyloxy, alkylcarbonyloxy, alkoxycarbonyl, cyano, methoxy, ethoxy, and the like.

Examples of substituents that R ¹¹ may have include the same substituents as the above-mentioned first substituents that Sp has.

In the above formula, when two or more R ¹¹ are not hydrogen atoms, the two R ¹¹ that are not hydrogen atoms can be selected from oxygen atoms, sulfur atoms ^, divalent nitrogen atom-containing groups and methylene groups directly or through a single bond. Any one of the formed groups forms a ring structure.

n ⁸ is 4.

Specific examples of unit D include units composed of monomers such as 4-hydroxyphenyl (meth)acrylate.

When the above-mentioned polymer contains the above-mentioned unit D, the acid generation efficiency can be improved.

The unit C is preferably a unit in which R ¹ in the above formula (1) is a hydrogen atom or a linear alkyl group, and L is a carbonyloxy group or a phenylene diyl group.

In addition, from the viewpoint of LWR, unit D preferably has L as a carbonyloxy group or a carbonylamino group, Sp as a direct bond, ^R1 as a methyl group, and the methyl group as the first substituent having an alkane having 1 to 4 carbon atoms. at least one unit of a radical, a halogen atom and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

One aspect of the present invention may contain two or more types of the above-mentioned units D in the above-mentioned polymer.

(Unit E)

One type of polymer of the present invention preferably further contains, in addition to the above units A to D, an organometallic compound unit E (hereinafter) having a metal atom selected from the group consisting of Sn, Sb, Ge, Bi and Te. Called "Unit E").

The metal atoms contained in the above-mentioned unit E are not particularly limited as long as they have high absorption power for EUV or electron beams, and may be atoms from Groups 10 to 16 of the periodic table of elements other than the above-mentioned metal atoms.

The above unit E is preferably an alkyl tin and an aryl tin, an alkyl antimony and an aryl antimony, an alkyl germanium and an aryl germanium, or an alkyl bismuth and an aryl bismuth structure bonded to * in the above formula (1) at any position part of the unit.

Unit E has a high secondary electron generation efficiency generated by EUV irradiation and can improve the decomposition efficiency of unit A and unit B mentioned above. The unit E is not particularly limited as long as it contains the above-mentioned metal atoms with high EUV absorbing power. Specific examples thereof include the units shown below.

Preferably, R ^12a in the above general formula is each independently selected from the group consisting of a hydrogen atom and an alkyl group. The alkyl group of R ^12a may have a substituent.

Examples of the above-mentioned alkyl groups include linear or branched ones having 1 to 5 carbon atoms, such as methyl, ethyl, isopropyl, n-isopropyl, sec-butyl, tert-butyl, n-butyl, and pentyl. of alkyl.

Examples of substituents that the alkyl group may have include hydroxyl, sulfonyloxy, alkylcarbonyloxy, alkoxycarbonyl, cyano, methoxy, ethoxy, and the like.

In the above formula, when two or more R ^12a are not hydrogen atoms, the two R ^12a that are not hydrogen atoms can be selected from the group consisting of oxygen atoms ^, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups directly or through a single bond. Any one of the formed groups forms a ring structure.

In the above formula, two or more R ^12b may form a ring structure through a single bond directly or through any one selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group.

n ⁹ is an integer from 0 to 4.

In the above general formula, R ^12b is a straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms that may have a substituent; a straight-chain, branched or cyclic carbon atom that may have a substituent. An alkenyl group with 1 to 6 carbon atoms; an aryl group with 6 to 14 carbon atoms that may have a substituent; a heteroaryl group with 4 to 12 carbon atoms that may have a substituent; and any one of the groups formed by direct bonding .

Examples of the linear, branched or cyclic alkyl group for R ^12b include the same options as the alkyl group for R ^2b described above.

Examples of the linear, branched or cyclic alkenyl group of R ^12b include the same options as the alkenyl group of R ^2b described above.

Examples of the aryl group having 6 to 14 carbon atoms in R ^12b include the same options as the aryl group in R ^2b described above. Examples of the heteroaryl group having 4 to 12 carbon atoms for R ^12b include the same options as the heteroaryl group for R ^2b described above.

Two or more R ^12a may form a ring structure through a single bond directly or through any one selected from the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group. In addition, any two of the three R ^12b may be bonded to each other and form a ring structure together with these bonded metal atoms.

Examples of substituents that R ^12a and R ^12b may have include the same options as the first substituent that Sp has.

Unit E specifically includes 4-vinylphenyl-triphenyltin, 4-vinylphenyl-tributyltin, 4-isopropenylphenyl-triphenyltin, and 4-isopropenylphenyl. -Trimethyltin, trimethyltin acrylate, tributyltin acrylate, triphenyltin acrylate, trimethyltin methacrylate, tributyltin methacrylate, triphenyltin methacrylate, 4-vinylphenyl -Diphenylantimony, 4-isopropenylphenyl-diphenylantimony, 4-vinylphenyl-triphenylgermane, 4-vinylphenyl-tributylgermane, 4-isopropenyl Units composed of monomers such as phenyl-triphenylgermane and 4-isopropenylphenyl-trimethylgermane.

By containing the unit E, the polymer can increase the secondary electron generation efficiency when irradiated with particle beams or electromagnetic waves.

The above-mentioned unit E is preferably one in which R ¹ in the above-mentioned formula (1) is a hydrogen atom or a linear alkyl group, L carbonyloxy group or phenylene diyl group.

In addition, from the viewpoint of LWR, the above-mentioned unit E preferably has L being a carbonyloxy group or a carbonylamino group, Sp being a direct bond, R ¹ being a methyl group, and the methyl group having 1 to 4 carbon atoms in the above-mentioned first substituent. At least one unit of an alkyl group, a halogen atom and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

In one aspect of the present invention, the polymer may have 2 or more of the units E.

(Unit F)

One aspect of the polymer of the present invention preferably further has unit F, and unit F is represented by the following formula (VIII) having a halogen atom.

In the above-mentioned general formula (VIII), R ¹ , L and Sp are each preferably selected from the same options as R ¹ , L and Sp of the above-mentioned general formula (1).

R ^h is selected from linear, branched or cyclic alkyl groups with 1 to 12 carbon atoms that may have substituents; linear, branched or cyclic alkyl groups with 1 to 12 carbon atoms that may have substituents. Alkyleneoxy; straight-chain, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have substituents; straight-chain, branched or cyclic alkenyl group having 1 to 12 carbon atoms which may have substituents Any one of the group consisting of an alkenyleneoxy group; an aryl group with 6 to 14 carbon atoms that may have a substituent; and a heteroaryl group with 4 to 12 carbon atoms that may have a substituent, and the carbon atom is substituted Part or all of the hydrogen atoms are replaced by fluorine atoms or iodine atoms.

Examples of the alkyl group, alkenyl group, alkylene group of alkyleneoxy group, alkenylene group of alkenyleneoxy group, aryl group and heteroaryl group of R ^h include the same options as the above-mentioned Sp.

In addition, these substituents may include the same options as the substituents of Sp.

Specific examples of unit F include units obtained from the following monomers.

The above-mentioned unit F is preferably such that R ¹ in the above-mentioned formula (VIII) is a hydrogen atom or a linear alkyl group, L carbonyloxy group, carbonylamino group or phenylene diyl group.

In addition, from the viewpoint of LWR, the above-mentioned unit F preferably has L being a carbonyloxy group or a carbonylamino group, Sp being a direct bond, R ¹ being a methyl group, and the methyl group having 1 to 4 carbon atoms in the above-mentioned first substituent. At least one unit of an alkyl group, a halogen atom and an aryl group. R ¹ having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

In one aspect of the present invention, the polymer may contain two or more types of units F.

(other units)

As long as the effects of the present invention are not impaired, one type of polymer of the present invention may have units commonly used in resist compositions in addition to the above-mentioned units A to F.

For example, a unit having a skeleton (such as an ether group, a lactone skeleton, an ester group, a hydroxyl group, an epoxy group, a glycidyl group, an oxetanyl group, etc.) in the * part of the above formula (1) can be exemplified. Hereinafter referred to as "unit G").

In addition, a unit having a skeleton having an alcoholic hydroxyl group in the * part of the above formula (1) (hereinafter referred to as "unit H") can be cited. This unit H is different from the above-mentioned units A~G. The above-mentioned polymer contains the above-mentioned unit H and is preferable because it tends to increase the intramolecular cross-linking reaction percentage.

When the acid generated ^by the unit ^A _is a strong acid, that _is , when Polymerization is preferred.

One aspect of the polymer of the present invention may have unit I represented by the following general formula (IX). Unit I It is a different unit from the above-mentioned units A~H. When a polymer of one type of the present invention has unit I, the main chain of the polymer is easily cut by the action of free radicals generated by irradiation of particle beams or electromagnetic waves, and the polymer chain at the exposure boundary can be shortened, thereby reducing the The effect of LWR.

In the above general formula (IX), each substituent is preferably as follows:

R ¹⁰ is any one selected from the group consisting of a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group with 1 to 6 carbon atoms. One, at least one hydrogen atom in the above-mentioned alkyl group and alkenyl group in R ¹ may be substituted by a substituent, L ¹⁰ is a direct bond, and R ^c is an aryl group with 6 to 12 carbon atoms that may have the above-mentioned first substituent. . The alkyl group having 1 to 6 carbon atoms and the alkenyl group having 1 to 6 carbon atoms in R ¹⁰ are selected from the same group as the alkyl group having 1 to 6 carbon atoms and the alkenyl group having 1 to 6 carbon atoms in R ¹ . options.

Alternatively, R ¹⁰ is a methyl group and the methyl group has at least one of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group in the first substituent, L is a carbonyloxy group or a carbonylamino group, and R ^c is A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom or the above-mentioned first substituent.

In addition, L is a carbonyloxy group or a carbonylamino group, R ^c is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R ¹⁰ is a methyl group, and the methyl group has the above-mentioned first substitution The base is at least one unit of an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an aryl group. R ¹⁰ having the above-mentioned first substituent is particularly preferably an ethyl group, isopropyl group, butyl group, halogenated methyl group (fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc.), benzyl group, or the like.

In addition, the above-mentioned unit I is a unit different from the above-mentioned units A to H.

The unit I is a unit derived from, for example, the following monomers: α-methylstyrene derivatives, 2-ethyl acrylic acid and its ester derivatives, 2-benzyl acrylic acid and its ester derivatives, 2-propylacrylic acid and its ester derivatives, 2-isopropylacrylic acid and its ester derivatives, 2-butylacrylic acid and its ester derivatives, 2-sec-butylacrylic acid and its ester derivatives, 2-fluoromethyl Acrylic acid and its ester derivatives, 2-chloromethacrylic acid and its ester derivatives, 2-bromomethacrylic acid and its ester derivatives, 2-iodomethacrylic acid and its ester derivatives, etc.

Specific examples of the unit I include units derived from the monomers shown below.

One aspect of the polymer of the present invention may have unit J represented by the following general formula (X).

In the above formula (X), R ¹ , L and Sp are each selected from the same options as R ¹ , L and Sp of the general formula (1).

R ^d is selected from linear, branched or cyclic alkylsilyl groups with 1 to 12 carbon atoms that may have substituents; linear, branched or cyclic alkylsilyl groups with 1 to 12 carbon atoms that may have substituents. 12 alkoxysilyl groups; straight-chain, branched or cyclic alkenylsilyl groups with 1 to 12 carbon atoms which may have substituents; straight-chain, branched or cyclic alkenyl silyl groups which may have substituents Alkenyloxysilyl group with 1 to 12 carbon atoms. Siloxane bonds formed by replacing part of the carbon atoms with silicon atoms and oxygen atoms so that the bonded hydrogen or carbon is replaced by oxygen may also be included.

The above-mentioned unit J can contain silicon, thereby improving the etching resistance of oxygen plasma. Furthermore, when unit J in the polymer has a silane structure, the above-mentioned unit B reacts under the action of an acid catalyst to generate water, which hydrolyzes unit J into silanol to form siloxane bonding and cross-linking, which can improve sensitivity and It is preferred for the effect of substrate adhesion.

In addition, the above-mentioned unit J is a different unit from the above-mentioned units A to I.

Unit J may be a unit derived from the following monomers, which may be enumerated: 4-trimethylsilylstyrene, 4-trimethoxysilylstyrene, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 8-methacryloxyoctyltrimethyl Oxysilane ^{, 3-} (3,5,7,9,11,11,13,15-heptaisobutylpentacyclo[ ^{9,5,13,9,15,15,17,13} ] Siloxane-1-yl)propyl methacrylate, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methyldimethoxysilane, 8-acryloxyoctyltrimethoxysilane, 3-(3,5,7,9,11,11,13,15-heptaisobutylpentacyclo[9,5 , 1 ^{3, 9} , 1 ^{5, 15} , 1 ^{7, 13} ] octasiloxane-1-yl) propyl methacrylate, etc.

water soluble

One aspect of the resist composition of the present invention is characterized in that irradiation with particle beams or electromagnetic waves causes an intramolecular cross-linking reaction. Therefore, when a strong acid (X- is CF ₃ SO ₃ -, etc.) is used as the acid generated from the unit A, and an organic solvent aqueous solution is used as the developer, the units of the polymer of the present invention preferably do not contain other units having an acid-dissociable group. unit. The reason is that when the unit of the polymer of the present invention contains another unit having an acid-dissociable group, the solubility of the polymer in a water-soluble developer tends to increase due to the action of an acid generated by decomposition of the unit A.

Relative to the above-mentioned unit A, the molar ratio of the polymer in one aspect of the present invention is respectively: the above-mentioned unit B is preferably 0.2~5, the above-mentioned unit C is preferably 0~3, the above-mentioned unit D is preferably 0~2, and the above-mentioned unit D is preferably 0-2. The unit E is preferably 0 to 2, the unit F is preferably 0 to 2, the unit G is preferably 0 to 2, the unit H is preferably 0 to 2, the unit I is preferably 0 to 0.5, and the unit J is preferably 0 ~4.

By using the monomer components constituting each of the above units as raw materials, polymerization can be carried out by a general method. The polymer in one aspect of the present invention is obtained by adjusting the above mixing ratio.

<2>Resist composition

One aspect of the resist composition of the present invention is characterized by containing the above-mentioned polymer.

In addition to the above-mentioned polymer, components such as polysubstituted alcohol compounds, organic metal compounds, and organic metal complexes may be optionally contained. Each component is described below.

The blending amount of the above-mentioned polymer in the resist composition is preferably 70 to 100% by mass based on the total solid content.

(Multiple substituted alcohol compounds)

The resist composition of one aspect of the present invention may have a structure containing only the above-mentioned polymer, or may further contain other components in addition to the above-mentioned polymer, such as ethylene glycol, triethylene glycol, erythritol, Compounds with two or more hydroxyl groups in the molecule such as arabitol, 1,4-benzenedimethanol and 2,3,5,6-tetrafluoro-1,4-benzenedimethanol. By containing these components in the resist composition, the efficiency of the cross-linking reaction and the sensitivity to particle beams or electromagnetic waves can be improved.

(organometallic compounds and organometallic complexes)

The resist composition according to one aspect of the present invention preferably further contains an organic metal compound or an organic metal complex.

In order to sensitize the above unit A and the above unit B, it is preferable that the above metal is selected from the group consisting of Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In , Sn, Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra. species.

Examples of the organic metal compound include tetraaryltin, tetraalkyltin, bis(alkylphosphine)platinum, and the like.

Examples of the organic metal complex include hafnium (IV) acrylate, zirconium (IV) acrylate, bismuth (III) acrylate, bismuth (III) acetate, tin (II) oxalate, and the like.

The mixing amount of the organic metal compound and the organic metal complex in the resist composition is preferably 0 to 0.5 molar equivalents relative to the unit A.

(other ingredients)

As long as the effects of the present invention are not impaired, the resist composition according to one embodiment of the present invention may be mixed with other components in any embodiment. The ingredients that can be mixed are well-known additives. For example, quenchers such as fluorine-containing waterproof polymers and trioctylamine, surfactants, fillers, pigments, antistatic agents, flame retardants, and light stabilizers can be added. At least one of agents, antioxidants, ion trapping agents and solvents.

Examples of the fluorine-containing waterproof polymer include polymers commonly used in liquid immersion exposure processes, and polymers having a fluorine content greater than the above-mentioned polymers are preferred. Therefore, when a resist film is formed using a resist composition, the water-repellent property of the fluorine-containing waterproof polymer can cause the fluorine-containing waterproof polymer to be localized on the surface of the resist film.

<3> Preparation method of resist composition

The preparation method of one type of the resist composition of the present invention is not particularly limited, and the above-mentioned polymer and other optional components can be prepared by public methods such as mixing, dissolving, or kneading.

It can be obtained by suitably polymerizing the monomers constituting the unit A and the unit B, and if necessary, by The above-mentioned polymer is synthesized by suitably polymerizing monomers constituting other units by conventional methods. However, the method for producing the polymer according to the present invention is not limited to this.

<4>Manufacturing method of parts

One aspect of the present invention is a method for manufacturing a component, which includes the following steps: forming a resist film on a substrate using the resist composition; and exposing the resist film using a particle beam or an electromagnetic beam. a photolithographic step; and a patterning step of developing a photolithographic resist pattern on the exposed resist film.

Examples of the above-mentioned components include equipment, masks, and the like.

Examples of particle beams or electromagnetic waves used for exposure in the photolithography step include electron beams and EUV, respectively.

The amount of light irradiation varies depending on the type and mixing ratio of each component in the photocurable composition, the film thickness of the coating film, etc., but is preferably 1 J/cm ² or less or 1000 μC/cm ² or less.

When the resist composition is included as a sensitizing unit (unit C) in the polymer, or when it is included as a sensitizing compound, it is preferable to perform secondary exposure using ultraviolet rays or the like after irradiation with a particle beam or electromagnetic wave.

The method for manufacturing a component according to one aspect of the present invention preferably further includes the step of etching a coating film obtained by applying a composition for an inversion pattern so as to cover at least the recessed portion of the photoresist pattern, so that the photoresist pattern is etched. The step of exposing the surface of the resist pattern; and the step of removing the above-mentioned resist film on the above-mentioned exposed surface part of the resist pattern to obtain a reverse pattern.

As the composition for reversal pattern, a known composition for reversal pattern can be used, and examples thereof include, A composition containing a siloxane polymer described in International Publication No. WO2015/025665, etc.

In addition, one aspect of the present invention is a method for forming a reverse pattern, which includes the following steps:

A step of forming a resist film on a substrate using the above resist composition;

The photolithography step of exposing the above-mentioned resist film using particle beam or electromagnetic beam;

A patterning step of developing a photolithographic resist pattern on the exposed resist film is obtained.

In addition, one aspect of the present invention is a method for forming a reverse pattern, which includes the following steps:

A step of forming a resist film on a substrate using the above resist composition;

The photolithography step of exposing the above-mentioned resist film using particle beam or electromagnetic beam;

Obtaining a patterning step of developing a photolithographic resist pattern on the exposed resist film;

The step of etching the coating film obtained by applying the composition for reversal pattern to cover at least the recessed portion of the above-mentioned photoresist pattern, thereby exposing the surface of the above-mentioned photoresist pattern;

The step of removing the above-mentioned resist film from the above-mentioned exposed resist pattern surface portion to obtain a reverse pattern.

In addition to using the above resist composition, a general inversion pattern forming method can also be used.

The above-mentioned substrate is preferably an inorganic substrate such as Si, SiO ₂ , SiN, SiON, TiN, WSi, and BPSG (Boron Phosphorus Silicon Glass). For example, in the case of a device manufacturing method, SOG (SOG) coated with an organic antireflection film or the like is preferable. Spin on Glass) and other coating-based inorganic substrates.

In the case of the mask manufacturing method, the substrate is preferably an inorganic substrate such as Cr, CrO, CrON, MoSi ₂ , and SiO ₂ , and it is more preferable that the inorganic substrate has an EUV absorbing layer such as TaO. The substrate used to make the mask can have the same structure as the substrate used for a common mask. For example, in the case of a transmissive mask, it is preferably transparent to the transmitted light of the target, and in the case of a reflective mask, it is preferably transparent to the light of the target. (Electromagnetic waves such as EUV, etc.) have high reflectivity.

The development in the pattern forming step can use a commonly used developer. Examples of the developer include: alkaline developer, neutral developer, organic solvent developer, etc.

In addition, it is preferable to use a water-soluble developer containing a water-soluble organic solvent as a developer other than those mentioned above. The above-mentioned water-soluble organic solvent may be an organic compound having 1 or more carbon atoms mixed with water at any percentage. Specific examples include methanol, ethanol, isopropyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol, Propylene glycol monomethyl ether, triethylene glycol, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, diglyme, triglyme, acetonitrile, acetone, N, N- Dimethylformamide, dimethyl sulfoxide, formic acid, acetic acid, propionic acid, etc.

The above-mentioned water-soluble developer only needs to contain one or more water-soluble organic solvents to form an aqueous solution, and a water-insoluble organic solvent may be further mixed. Examples of the water-immiscible organic solvent include water-immiscible alcohols, water-immiscible ethers, water-immiscible nitriles, water-immiscible ketones, and water-immiscible esters. (such as ethyl acetate) and organic halogen compounds (such as methylene chloride), etc.

[Example]

Hereinafter, several aspects of the present invention will be described based on examples, but the present invention is not limited to these examples in any way.

<Synthesis of compound A1 constituting unit A>

(Synthesis Example 1) Synthesis of dibenzothiophene 9-oxide

7.0 g of dibenzothiophene was dissolved in 21.0 g of formic acid and the temperature was adjusted to 35°C. Here, 4.1 g of 35% by mass hydrogen peroxide solution was added dropwise, and the mixture was stirred at 25° C. for 5 hours. After cooling, the reaction liquid was added dropwise to 50 g of pure water to precipitate a solid. The precipitated solid was filtered, washed twice with 20 g of pure water, and then recrystallized using acetone. After filtering and drying, 7.6 g of dibenzothiophene 9-oxide was obtained.

(Synthesis Example 2) Synthesis of 9-(4-hydroxyphenyl)dibenzothiophene iodide

4.0 g of dibenzothiophene 9-oxide and 2.8 g of phenol obtained in Synthesis Example 1 were dissolved in 16 g of methanesulfonic acid to bring the temperature to 25°C. Here, 1.5 g of phosphorus pentoxide was added and the mixture was stirred at room temperature for 15 hours. Then, 60 g of pure water was added and the mixture was stirred for 5 minutes. The mixture was washed twice with 20 g of ethyl acetate and separated into liquids. To the obtained aqueous layer, 3.6 g of potassium iodide and 30 g of methylene chloride were added, and the mixture was stirred at room temperature for 2 hours. The organic layer obtained by liquid separation was washed 4 times with 40 g of pure water. The recovered organic layer was concentrated, and 100 g of diisopropyl ether was added dropwise to precipitate a solid. The precipitated solid was filtered and dried to obtain 6.6 g of 9-(4-hydroxyphenyl)dibenzothiophene iodide.

(Synthesis Example 3) Synthesis of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate

6.0 g of 9-(4-hydroxyphenyl)dibenzothiophene iodide and 2.3 g of dimethyl sulfate obtained in the above Synthesis Example 2 were dissolved in 15 g of methanol to 25°C, and stirred at room temperature for 4 hours. 45 g of ethyl acetate was added to precipitate a solid. The precipitated solid was filtered and dried to obtain 4.9 g of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate.

(Synthesis Example 4) Synthesis of 9-(4-methacryloxyphenyl)dibenzothiophene-methylsulfate (compound A1)

4.0 g of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate and 1.9 g of methacrylic acid chloride obtained in the above Synthesis Example 3 were dissolved in 25 g of methylene chloride to bring the temperature to 25°C. Add dropwise A solution of 1.4 g of ethylamine dissolved in 7 g of methylene chloride was stirred at 25°C for 2 hours. After stirring, add 20 g of pure water and continue stirring for 10 minutes before performing liquid separation. After washing the organic layer twice with 20 g of pure water, the concentrated and recovered organic layer was added dropwise to 60 g of diisopropyl ether to precipitate a solid. The precipitated solid was filtered and dried to obtain 3.0 g of 9-(4-methacryloyloxyphenyl)dibenzothiophene-methylsulfate (compound A1).

<Synthesis of compound A2 constituting unit A>

(Synthesis Example 5) Synthesis of 9-(4-propenyloxyphenyl)dibenzothiophene-methylsulfate (compound A2)

【Chemical 24】

Except using acrylic acid chloride instead of methacrylic acid chlorine, the same operation as in Synthesis Example 4 was performed to obtain 4.4 g of 9-(4-acrylyloxyphenyl)dibenzothiophene-methyl sulfate (compound A2).

<Synthesis of compound A3 constituting unit A>

(Synthesis Example 6) Synthesis of 9-(4-methacryloxyphenyl)dibenzothiophene-benzoate (Compound A3)

4.0 g of 9-(4-methacrylyloxyphenyl)dibenzothiophene-methylsulfate and 2.9 g of sodium salicylate obtained in the above Synthesis Example 4 were added to 25 g of methylene chloride and 20 g of pure water. , stirred at 25°C for 2 hours, separated the liquids, and concentrated the recovered organic layer. After the solvent was distilled off and the organic layer was obtained, Purification by column chromatography (dichloromethane/methanol=80/20 (volume ratio)) gave 9-(4-methacryloxyphenyl)dibenzothiophene-benzoate (compound A3) 3.4g.

<Synthesis of compound A4 constituting unit A>

(Synthesis Example 7) Synthesis of (4-hydroxy)phenyldiphenylsulfonate iodine

The same operation as in Synthesis Example 2 was performed except that diphenyl sulfoxide was used instead of dibenzothiophene 9-oxide to obtain 5.9 g of iodine (4-hydroxyphenyl) diphenylsulfonate.

(Synthesis Example 8) Synthesis of (4-methacryloyloxyphenyl)diphenylsulfonic acid-trifluoromethanesulfonate (compound A4)

Use (4-hydroxyphenyl)diphenylsulfonic acid-methylsulfate instead of 9-(4-hydroxyphenyl)dibenzothiophenemethylsulfate, and use silica gel column chromatography (dichloromethane/methanol=9 /1) Instead of solid precipitation from diisopropyl ether, the same operation as in Synthesis Example 4 was performed to obtain (4-methacryloyloxyphenyl)diphenylsulfonic acid-trifluoromethanesulfonic acid. Salt (compound A4) 3.8g.

<Synthesis of compound A5 constituting unit A>

(Synthesis Example 9) Synthesis of (4-methacryloyloxyphenyl)diphenylsulfonic acid benzoate (compound A5)

In addition to replacing 9-(4-methacryloxyphenyl)dibenzothiophene-methylsulfate with (4-methacryloxyphenyl)phenyldiphenylsulfonate methylsulfate, proceed with The same operation as in Synthesis Example 6 above was performed to obtain 3.5 g of (4-methacryloyloxyphenyl)diphenylsulfonic acid methyl sulfate (compound A5).

<Synthesis of compound A6 constituting unit A>

(Synthesis Example 10) Synthesis of 5-(4-hydroxynaphthyl)tetramethylenesulfonic acid trifluoromethanesulfonic acid

The same operation as in Synthesis Example 2 was performed except that tetramethylene sulfoxide was used instead of dibenzothiophene 9-oxide, 1-naphthol was used instead of phenol, and potassium triflate was used instead of potassium iodide to obtain 5- (4-Hydroxynaphthyl)tetramethylenesulfonic acid trifluoromethanesulfonic acid 4.7g.

(Synthesis Example 11) Synthesis of 5-(4-methacrylyloxynaphthyl)tetramethylenesulfonic acid trifluoromethanesulfonic acid (Compound A6)

The same procedure as in Synthesis Example 4 was performed except that 5-(4-hydroxynaphthyl)tetramethylenesulfonic acid trifluoromethanesulfonic acid was used instead of 9-(4-hydroxyphenyl)dibenzothiophenemethylsulfate. operation, we get (5-(4 -Methacryloyloxynaphthyl)tetramethylenesulfonic acid trifluoromethanesulfonic acid (compound A6) 5.1 g.

<Synthesis of compound A7 constituting unit A>

(Synthesis Example 12) Synthesis of (4-aminophenyl)diphenylsulfonium bromide

Add 2.0 g of tetrahydrofuran, 0.4 g of magnesium and 1,2-dibromoethane into the pre-dried flask to activate the magnesium. After confirming that magnesium has been activated, the solution was heated to 50°C, and a solution of 3.0g of 4-bromo-N,N-bis(trimethylsilyl)aniline dissolved in 6.0g of THF was added dropwise, and the solution was heated at 50°C. Stir for 5 hours to obtain a THF solution of 4-[N, N-(bistrimethylsilyl)]aminophenyl magnesium bromide. Dissolve 1.9g of diphenyl sulfoxide, 1.8g of trimethylsilyl chloride and 0.8g of triethylamine in a solution of 9.5g of methylene chloride, and add dropwise 4-[N,N-(bistrimethyl After stirring the THF solution of aminophenyl magnesium bromide at 25°C for 1 hour, 30 g of a 10 mass% ammonium chloride aqueous solution was added at 5°C or lower and stirring was continued for 10 minutes. Thereafter, dichloromethane was removed by liquid separation distillation, and 20 g of methanol and 1.6 g of triethylamine were added. After stirring for 2 hours, the solvent was distilled off to obtain 3.1 g of (4-aminophenyl)diphenylsulfonium bromide.

(Synthesis Example 13) Synthesis of (4-methacryloylaminophenyl)diphenylsulfonium bromide

Except using (4-aminophenyl)diphenylsulfonium bromide instead of 9-(4-hydroxyphenyl)dibenzothiophene methyl sulfate, the same operation as in Synthesis Example 4 was performed to obtain (4-methyl 3.8 g of acryloyl aminophenyl)diphenyl sulfonium bromide.

(Synthesis Example 14) Synthesis of (4-methacryloylaminophenyl)diphenylsulfonic acid methyl sulfate (compound A7)

The same operation as in Synthesis Example 3 was performed except that (4-methacrylolaminophenyl)diphenylsulfonium bromide was used instead of 9-(4-hydroxyphenyl)dibenzothiophene iodide to obtain ( 2.7 g of 4-methacryloyl aminophenyl)diphenylsulfonic acid methyl sulfate.

<Synthesis of compound B1 constituting unit B>

(Synthesis Example 15) Synthesis of 2,4-dimethoxy-2’-hydroxybenzyl alcohol

Dissolve 6.0g of 2,4-dimethoxy-4-hydroxybenzophenone in 32g of THF, add 2.2g of lithium aluminum hydride, and stir at room temperature for 3 hours. After confirming the generation of hydrogen, add 6g of pure water and continue stirring. 10 minutes. After adding 5% sodium oxalate aqueous solution and stirring for 10 minutes, 30 g of ethyl acetate was added for liquid separation, washed three times with 10 g of water, and the recovered organic layer was concentrated to obtain 2,4-dimethoxy-2'-hydroxybis. Benzyl alcohol 5.9g.

(Synthesis Example 16) Synthesis of 2,4-dimethoxy-2’-methacryloxyhydroxybenzyl alcohol (Compound B1)

物B1)

Object B1)

4.0 g of 2,4-dimethoxy-2'-hydroxybenzyl alcohol and 4.2 g of methacrylic anhydride were dissolved in 40 g of dichloromethane to bring the temperature to 25° C., and 2.8 g of triethylamine was dissolved in dichloromethane by dropping A solution of 7 g of methane was stirred at 25°C for 2 hours, then 20 g of pure water was added and the mixture was stirred for 10 minutes and then separated. After washing the organic layer twice with 20 g of pure water, the recovered organic layer was concentrated and the solvent was distilled off. The resulting organic layer was purified by column chromatography (ethyl acetate/hexane = 15/85 (volume ratio)) to obtain 2.6 g of 2,4-dimethoxy-2'-methacryloxyhydroxybenzyl alcohol (compound B1).

<Synthesis of compound B2 constituting unit B>

(Synthesis Example 17) Synthesis of 2-hydroxybenzyl alcohol

The same procedure as in Synthesis Example 15 was performed except that 2-hydroxybenzophenone was used instead of 2,4-dimethoxy-4-hydroxybenzophenone to obtain 3.5 g of 2-hydroxybenzyl alcohol.

(Synthesis Example 18) Synthesis of 2-methacryloxyhydroxybenzyl alcohol (Compound B2)

【Chemical 37】

2-hydroxybenzyl alcohol was used instead of 2,4-dimethoxy-2'-hydroxydiphenyl alcohol, and the residue obtained by concentration was subjected to column chromatography (ethyl acetate/hexane = 10/90 (volume ratio) ) except for purification, the same operation as in Synthesis Example 16 was performed to obtain 3.5 g of 2-methacryloyloxyhydroxybenzyl alcohol (Compound B2).

<Synthesis of compound B3 constituting unit B>

(Synthesis Example 19) Synthesis of 1-(4-hydroxyphenyl)ethanol

The same procedure as in Synthesis Example 15 was performed except that 4-hydroxyacetophenone was used instead of 2-hydroxybenzophenone to obtain 2.7 g of 1-(4-hydroxyphenyl)ethanol.

(Synthesis Example 20) Synthesis of 1-(4-methacryloxyphenyl)ethanol (Compound B3)

2-hydroxybenzyl alcohol was used instead of 2,4-dimethoxy-2'-hydroxydiphenyl alcohol, and the residue obtained by concentration was subjected to column chromatography (ethyl acetate/hexane=10/90 (volume ratio )) except for purification, the same operation as in Synthesis Example 16 was performed to obtain 3.5 g of 2-methacryloyloxyhydroxybenzyl alcohol (compound B3).

<Synthesis of compound B4 constituting unit B>

(Synthesis Example 21) Synthesis of 2,4-dimethoxy-4’-(2-vinyloxy)ethoxybenzophenone

4.0g of 2,4-dimethoxy-4'-hydroxy-benzophenone, 4.8g of 2-chloroethyl vinyl ether and 6.4g of potassium carbonate were dissolved in 24g of dimethylformamide, and the mixture was Stir at 110°C for 15 hours. Afterwards, the mixture was cooled to 25°C, 60g of water was added, stirring was continued, and then extracted with 24g of toluene. The organic layer recovered after washing three times with 10g of water was concentrated, and the obtained organic layer solvent was distilled off. After removal, it was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybis Benzophenone 5.4g.

(Synthesis Example 22) Synthesis of 2,4-dimethoxy-4’-(2-hydroxy)ethoxybenzophenone

Dissolve 5.4g of 2,4-dimethoxy-4'-(2-vinyloxy)ethoxybenzophenone, 0.42g of pyridinium-p-toluenesulfonic acid and 4.2g of pure water in 36g of acetone, The mixture was stirred at 35° C. for 12 hours, and 3% by mass sodium carbonate aqueous solution was added. The mixture was further stirred and extracted with 42 g of ethyl acetate. The organic layer recovered after washing three times with 10 g of water was concentrated to obtain 2,4 -Dimethoxy-4'-(2-hydroxy)ethoxybenzophenone 4.3g.

(Synthesis Example 23) Synthesis of 2,4-dimethoxy-4’-(2-hydroxy)ethoxybenzyl alcohol

The same operation as in Synthesis Example 15 above was performed except that 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone was used instead of 2-hydroxybenzophenone to obtain 2,4 -Dimethoxy-4'-(2-hydroxy)ethoxybenzyl alcohol 2.7g.

(Synthesis Example 24) Synthesis of 2,4-dimethoxy-4’-(2-methacryloxy)ethoxybenzenemethanol (Compound B4)

2-hydroxybenzyl alcohol was used instead of 2,4-dimethoxy-2'-hydroxydiphenyl alcohol, and the residue obtained by concentration was subjected to column chromatography (ethyl acetate/hexane=10/90 (volume ratio )) except for purification, the same operation as in Synthesis Example 16 was performed to obtain 2,4-dimethoxy-4'-(2-methacryloxy)ethoxybenzyl alcohol (compound B4) 3.5 g.

<Synthesis of compound B5 constituting unit B>

(Synthesis Example 25) Synthesis of 2-ethylacrylyl chloride

【Chemical 44】

5.0 g of 2-ethylacrylic acid was dissolved in 35 g of methylene chloride to bring the temperature to 50° C., 5.1 g of oxalic acid chloride was added dropwise over 10 minutes, and stirred at the reflux temperature for 2 hours to obtain dimethyl chloride of 2-ethylacrylic acid. Methyl chloride solution 26.3g.

(Synthesis Example 26) Synthesis of 2,4-dimethoxy-2’-(2-ethyl)propenyloxyhydroxybenzyl alcohol (compound B5)

Except using 2-ethylacrylyl chloride instead of methacrylic anhydride, the same operation as the above-mentioned Synthesis Example 16 was performed to obtain 2,4-dimethoxy-2'-(2-ethyl)propenyloxyhydroxybis Benzyl alcohol (compound B) 2.4g.

<Synthesis of compound B6 constituting unit B>

(Synthesis Example 27) Synthesis of 2-fluoromethacrylic acid chloride

The same method as in Synthesis Example 22 was carried out except that 2-fluoromethacrylic acid was used instead of 2-ethylacrylic acid to obtain 31.4 g of a methylene chloride solution of 2-fluoromethacrylic acid chloride.

(Synthesis Example 28) Synthesis of 2,4-dimethoxy-2’-(2-ethyl)propenyloxyhydroxybenzyl alcohol (compound B6)

Except using 2-fluoromethacrylic acid chloride instead of methacrylic anhydride, the same operation as in Synthesis Example 16 was performed to obtain 2,4-dimethoxy-2'-(2-fluoromethyl)acryloxy Hydroxybenzyl alcohol (compound B6) 2.8g.

<Synthesis of compound C1 constituting unit C>

(Synthesis Example 29) Synthesis of 1-[4-(2-methacryloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (compound C1)

4.0 g of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure2959) and 4.6 g of methacrylic anhydride were dissolved in di 40g of methyl chloride was brought to 25°C, and a solution of 3.0g of triethylamine dissolved in 7g of methylene chloride was added dropwise and stirred at 25°C for 2 hours. Then, 20g of pure water was added and stirring was continued for 10 minutes before liquid separation. The organic layer recovered after washing twice with 20 g of pure water was concentrated, and the solvent was distilled off. The resulting organic layer was then purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 1 -[4-(2-Methacrylyloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (compound C1) 4.9 g.

<Synthesis of compound C2 constituting unit C>

(Synthesis Example 30) Synthesis of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone

2.0 g of magnesium and 10 g of THF were added to a flask from which the moisture had been removed beforehand, and 10.0 g of 4-(2-ethoxy)ethoxyphenyl bromide was dissolved in 50.0 g of THF. The solution was added dropwise over 1 hour at room temperature. solution. After the dropwise addition, after stirring at room temperature for 1 hour, the obtained 4-(2-ethoxy)ethoxyphenyl magnesium bromide solution was added dropwise to the added pivalic acid chloride at 5°C for 30 minutes. 9.8g and THF40g in a flask. After the dropwise addition, stir for 30 minutes, add 150g of 3% hydrochloric acid, and continue stirring for 10 minutes. Thereafter, THF was distilled off, extraction was performed with 150 g of ethyl acetate, liquid separation was performed, and the obtained organic layer was washed three times with 60 g of pure water. Thereafter, the solvent was distilled off and the organic layer obtained by liquid separation was purified by column chromatography (ethyl acetate/hexane = 20/80 (volume ratio)) to obtain 1-(4-hydroxyphenyl)-2,2 -Dimethyl-1-propanone 5.8g.

(Synthesis Example 31) Synthesis of 1-(4-methacryloxyphenyl)-2,2-dimethyl-1-propanone (compound C2)

4.0 g of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone and 4.1 g of methacrylic anhydride obtained in the above Synthesis Example 30 were dissolved in 32 g of methylene chloride to bring the temperature to 25°C. , a solution of 2.7 g of triethylamine dissolved in 7 g of methylene chloride was added dropwise, and after stirring at 25° C. for 2 hours, 20 g of pure water was added and stirring was continued for 10 minutes before liquid separation. Concentrated organic matter recovered after washing twice with 20g of pure water layer, the solvent was distilled off and the obtained organic layer was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) to obtain 1-(4-methacrylyloxyphenyl)- 4.6 g of 2,2-dimethyl-1-propanone (compound C2).

<Synthesis of compound C3 constituting unit C>

(Synthesis Example 32) Synthesis of 1-(4-propenyloxyphenyl)-2,2-dimethyl-1-propanone (compound C3)

Except using acryl chloride instead of methacrylic anhydride, the same operation as in Synthesis Example 13 was performed to obtain 1-(4-acrylyloxyphenyl)-2,2-dimethyl-1-propanone (compound C3 )5.3g.

<Synthesis of compound C4 constituting unit C>

(Synthesis Example 33) Synthesis of 1-(6-hydroxynaphthalene-2-yl)-2,2-dimethyl-1-propanone

The same operation as in Synthesis Example 30 was performed except that 2-bromo-6-(2-ethoxy)ethoxynaphthalene was used instead of 4-(2-ethoxy)ethoxyphenyl bromide to obtain 1 -(6-Hydroxynaphthalen-2-yl)-2,2-dimethyl-1-propanone 6.9g.

(Synthesis Example 34) Synthesis of 1-(6-methacryloxynaphthalene-2-yl)-2,2-dimethyl-1-propanone (compound C4)

In addition to using 1-(6-hydroxynaphth-2-yl)-2,2-dimethyl-1-propanone instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, The same operation as in Synthesis Example 30 was carried out to obtain 5.3 g of 1-(6-methacryloxynaphthalene-2-yl)-2,2-dimethyl-1-propanone (compound C4).

<Synthesis of compound C5 constituting unit C>

(Synthesis Example 35) Synthesis of 1-[4-(2-hydroxyethoxy)phenyl]-2,2-dimethyl-1-propanone

The same operation as in Synthesis Example 13 was performed except that 4-(2-ethoxy)ethoxyphenyl bromide was used instead of 4-(2-ethoxy)ethoxyphenyl bromide to obtain 1 -[4-(2-hydroxyethoxy)phenyl]-2,2-dimethyl-1-propanone 6.3g.

(Synthesis Example 36) Synthesis of 1-[4-(2-methacrylyloxy)ethoxyphenyl]-2,2-dimethyl-1-propanone (compound C5)

In addition to using 1-(2-hydroxyethoxyphenyl)-2,2-dimethyl-1-propanone instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, The same operation as in Synthesis Example 31 was performed to obtain 5.6 g of 1-[4-(2-methacrylyloxy)ethoxyphenyl]-2,2-dimethyl-1-propanone (compound C5). .

<Synthesis of compound C6 constituting unit C>

(Synthesis Example 37) Synthesis of phenylglyoxylic acid chloride

5.0 g of phenyglyoxylic acid was dissolved in 35 g of anisole to bring the temperature to 50°C. 5.1 g of oxalic acid chloride was added dropwise over 10 minutes, and the mixture was stirred at 50°C for 2 hours. After distilling off excess oxalyl chloride at 70° C., anisole was distilled off under a reduced pressure environment and concentrated to obtain 26.3 g of an anisole solution of phenylglyoxylic acid chloride.

(Synthesis Example 38) Synthesis of 1-(4-methoxyphenyl)-2-phenylethanedione

25.0 g of the anisole solution of phenylglyoxylate chloride obtained in Synthesis Example 36 was dissolved in 35 g of methylene chloride to bring the temperature to 0°C, and 4.3 g of aluminum chloride was added and stirred at 0°C for 2 hours. Add 35 g of pure water, stir for 10 minutes, and then separate the liquid. The organic layer recovered after being concentrated and washed twice with 30 g of pure water was purified by column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) after the solvent was distilled off. to obtain 5.6 g of 1-(4-methoxyphenyl)-2-phenylethanedione.

(Synthesis Example 38) Synthesis of 1-(4-hydroxyphenyl)-2-phenylethanedione

5.0 g of 4-methoxybenzyl was dissolved in 95 ml of acetic acid, and 33.2 g of a 48 mass% HBr aqueous solution was added dropwise at 70° C. over 10 minutes, and then stirred at 110° C. for 70 hours. Thereafter, 150 g of water was added to crystallize, and the mixture was filtered, washed with 250 g of water, and dried to obtain 4.1 g of 1-(4-hydroxyphenyl)-2-phenylethanedione.

(Synthesis Example 39) Synthesis of 2,2-dimethoxy-1-(4-methacryloxyphenyl)ethan-1-one (compound C6)

4.0 g of 1-(4-hydroxyphenyl)-2-phenylethanedione and 0.10 g of sulfuric acid were dissolved in 12 g of methanol to bring the temperature to 25°C, and 2.2 g of trimethyl orthoformate was added dropwise and stirred for 3 hours. After adding 0.6 g of triethylamine at 30° C. and stirring for 5 minutes, the solvent was distilled off. After adding 25 g of acetonitrile, 4.5 g of triethylamine, and 0.11 g of dimethylaminopyridine to the obtained residue, 6.8 g of methacrylic anhydride diluted with 5.0 g of acetonitrile was added dropwise at room temperature. After the dropwise addition, the mixture was stirred at 25° C. for 2 hours, and then 64 g of a 3 mass% NaHCO ₃ aqueous solution was added and stirred for 5 minutes. Thereafter, the organic layer recovered was extracted and concentrated with 32 g of ethyl acetate, washed three times with 10 g of water, and the solvent was distilled off. The resulting organic layer was then subjected to column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)). After purification, 4.3 g of 2,2-dimethoxy-1-(4-methacryloxyphenyl)ethan-1-one (compound C6) was obtained.

In addition to using 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, The same operation as in Synthesis Example 24 was performed to obtain 3.7 g of 2,2-dimethoxy-1-(4-methacryloxyphenyl)ethan-1-one (compound C6).

<Synthesis of compound C7 constituting unit C>

(Synthesis Example 40) Synthesis of 2-benzyl acrylic acid chloride

【Chemical 61】

The same method as in Synthesis Example I was carried out except that 2-benzyl acrylic acid was used instead of 2-ethylacrylic acid to obtain 31.4 g of a methylene chloride solution of 2-benzyl acrylic acid chloride.

(Synthesis Example 41) Synthesis of 1-{4-[(2-benzyl)acryloxy)ethoxyphenyl]-2-hydroxy-2-methyl-1-propanone (compound C7)

The same method as in Synthesis Example 31 was carried out except that 2-benzyl acrylic acid was used instead of methacrylic anhydride to obtain 1-{4-[(2-benzyl)acryloxy)ethoxyphenyl]-2 -Hydroxy-2-methyl-1-propanone (compound C7) 5.2g.

<Synthesis of compound E1 constituting unit E>

(Synthesis Example 42) Synthesis of 4-vinylphenyl-triphenyltin (Compound E1)

1.2g of magnesium and 6g of THF were added to a flask from which water had been removed in advance, and a solution of 6.0g of 4-vinylbromobenzene dissolved in 12.0g of THF was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred for 1 hour, and the obtained 4-vinylphenylmagnesium bromide solution was added dropwise at 5° C. over 30 minutes to the flask to which 7.3 g of triphenyltin chloride and 36 g of THF had been added. After the dropwise addition, stir for 30 minutes, add 600g of 1% ammonium chloride aqueous solution, and continue stirring for 10 minutes. Thereafter, THF was distilled off, extracted with 60 g of toluene and separated, and the obtained organic layer was washed three times with 60 g of pure water. The solvent was distilled off and the organic layer obtained by liquid separation was purified by column chromatography (ethyl acetate/hexane = 5/95 (volume ratio)) to obtain 4-vinylphenyl-triphenyltin (compound E1) 5.6 g.

<Synthesis of compound E2 constituting unit E>

(Synthesis Example 43) Synthesis of 4-isopropenylphenyl-triphenyltin (compound E2)

The same procedure as in Synthesis Example 42 was performed except that 4-isopropenylbromobenzene was used instead of 4-vinylbromobenzene to obtain 7.1 g of 4-isopropenylphenyl-triphenyltin (compound E2).

<Synthesis of compound E3 constituting unit E>

(Synthesis Example 44) Synthesis of 4-vinylphenyl-tributyltin (Compound E3)

The same procedure as in Synthesis Example 42 was performed except that tributyltin chloride was used instead of triphenyltin chloride to obtain 5.1 g of 4-vinylphenyl-tributyltin (compound E3).

<Synthesis of compound E4 constituting unit E>

(Synthesis Example 45) Synthesis of 4-vinylphenyl-triphenylgermane (Compound E4)

The same procedure as in Synthesis Example 34 was performed except that triphenylgermanium chloride was used instead of triphenyltin chloride to obtain 3.1 g of 4-vinylphenyl-tributylgermane (compound E4).

<Synthesis of compound F1 constituting unit F>

(Synthesis Example 46) Synthesis of 1-trifluoromethyl-2-bromoethanol

6.0 g of 1-bromo-3,3,3-trifluoroacetone was dissolved in 28 g of THF, 0.3 g of lithium aluminum hydride was added, and the mixture was stirred at room temperature for 3 hours. While confirming the generation of hydrogen, 6 g of pure water was added and stirring was continued for 10 minutes. After adding 5% sodium oxalate aqueous solution and stirring for 10 minutes, 30 g of ethyl acetate was added for liquid separation, and the recovered organic layer was washed three times with 10 g of concentrated water to obtain 5.9 g of 1-trifluoromethyl-2-bromoethanol.

(Synthesis Example 47) Synthesis of 1-trifluoromethyl-2-methacryloxyethanol (Compound F1)

Dissolve 5.0 g of 1-trifluoromethyl-2-bromoethanol in 20 g of DMF, add 3.9 g of potassium carbonate and 3.3 g of methacrylic acid, and stir at 80° C. for 3 hours. Then, add 20 g of pure water and continue stirring for 10 minutes. After adding 30g of ethyl acetate for liquid separation, washing with 10g of 1% hydrochloric acid aqueous solution, washing the recovered organic layer three times with 10g of concentrated water, and passing it through column chromatography (ethyl acetate/hexane = 10/90 (volume ratio)) After purification, 4.2 g of 1-trifluoromethyl-2-methacryloxyethanol (compound F1) was obtained.

<Synthesis of compound F2 constituting unit F>

(Synthesis Example 48) Synthesis of 1,3,5-triiodo-phenyl methacrylate (Compound F2)

Except using 1,3,5-triiodophenol instead of 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, the same operation as in Synthesis Example 13 was performed to obtain 1,3, 4.3 g of 5-triiodo-phenyl methacrylate (compound F2).

<Synthesis of comparative compound b1>

(Synthesis Example 49) Synthesis of 1-(2,4-dimethoxy)phenyl-1-[4’-(2-hydroxy)ethoxyphenyl]-1,1-dimethoxymethane

Perform the same procedure as above except using 2,4-dimethoxy-4'-(2-hydroxy)ethoxybenzophenone instead of 1-(4-hydroxyphenyl)-2-phenylethanedione. The same operation as Synthesis Example 24 was performed to obtain 1-(2,4-dimethoxy)phenyl-1-[4'-(2-hydroxy)ethoxyphenyl]-1,1-dimethoxymethane. 3.3g.

(Synthesis Example 50) 1-(2,4-dimethoxy)phenyl-1-[4'-(2-methacryloxy)ethoxyphenyl]-1,1-dimethoxy Synthesis of methane (comparison compound b1)

<Synthesis of comparative compound e1>

(Synthesis Example 51) Synthesis of 4-triphenylmethylphenyl methacrylate (comparative compound e1)

After substituting 4-triphenylmethylphenol for 1-(4-hydroxyphenyl)-2,2-dimethyl-1-propanone, the same operation as in Synthesis Example 13 above was performed to obtain 4-triphenylmethyl. 3.1 g of phenyl methacrylate (comparative compound e1).

<Synthesis of Polymer 1>

(Synthesis Example 52) Synthesis of Polymer 1

3.0 g of the compound A1 of the structural unit A, 2.2 g of the compound B1 of the structural unit B, 1.9 g of the compound C1 of the structural unit C, 3.0 g of the compound E1 of the structural unit E, and 0.61 g of the polymerization initiator Dimethyl-2,2'-azobis(2-methylpropionate) and 0.85 g of α-thioglycerol were dissolved in a mixed solution of 12 g of cyclohexanone and 19 g of γ-butyrolactone, and deoxygenated. The above solution was added dropwise to a mixed solution of 4 g of γ-butyrolactone and 4 g of cyclohexanone that had been heated to 70° C. over 4 hours, and the mixture was stirred for 2 hours and then cooled. After cooling, it was reprecipitated by adding dropwise to 90 g of ethyl acetate. After filtration, the mixture was stirred in 40 g of methanol for 10 minutes, filtered, and vacuum dried to obtain 7.3 g of the target polymer 1.

The unit ratio of the polymer is disclosed above, but the polymers in some embodiments of the present invention are not limited thereto.

<Synthesis of Polymers 2~15 and Comparative Polymers 1~2>

(Synthesis Example 53) Synthesis of Polymers 2 to 15 and Comparative Polymers 1 to 2

The above-mentioned compounds A1 to A6 constituting unit A, compounds B1 to B4 constituting unit B, compounds C1 to C6 constituting unit C, compounds constituting unit D, and compounds E1 to E4 constituting unit E are appropriately combined by imitating the above synthesis example 52. , compounds F1 to F4 constituting unit F, comparative compound b1, and comparative compound e1, polymers 2 to 11 and comparative polymers 1 to 2 were synthesized. The details of each polymer synthesized are shown in Table 1.

Compound D: 4-hydroxyphenyl methacrylate

Compound F3: 2-Perfluorobutylethyl methacrylate

Compound F4: 3,5-bis(2,2,2-trifluoro-1-hydroxy-1-trifluoromethylethyl)cyclohexyl methacrylate

<Preparation of Resist Composition>

400 mg of any of the above polymers was dissolved in a solvent of cyclohexanone, ethyl lactate and γ-butyrolactone mixed in a ratio of 5:5:1 to prepare the antibodies of Examples 1 to 10 and Comparative Examples 1 to 2. Etch composition samples 1 to 12. The polymers used are shown in Table 2 and Table 3.

<Preparation of developer>

Acetonitrile is mixed with pure water so that the composition of acetonitrile is in the range of 0~80 mass%, and an acetonitrile aqueous solution with a minimum acetonitrile concentration is used as a developer for each polymer, so that the above polymer 1~ The 100 nm thin films prepared by resist composition samples 1 to 8 of 5, 9, 11 and comparative polymer 1 by spin coating dipping were completely dissolved within 30 seconds.

<EUV sensitivity evaluation: Examples 1 to 7 and Comparative Example 1>

A thin film with a film thickness of 100 nm was formed by dropping and spin coating on a 6-inch silicon wafer, and then baking it on a hot plate at 110°C for 1 minute. After the above film was irradiated with an EUV exposure device (Energetic EQ-10m) at 0.25-3.0 mJ/ ^cm2 , it was immersed in an acetonitrile aqueous solution prepared in advance to the lowest concentration of the unexposed part of each polymer for 60 seconds to develop. Then, it was immersed in pure water for 30 seconds and washed to obtain a 1×1cm ² pattern. The sensitivity (E ₀ ) was determined by measuring the film thickness of the obtained pattern using a contact film thickness meter (Surfcorder ET-200, manufactured by Kosaka Laboratory) and preparing a sensitivity curve. E ₀ is defined as the exposure amount when the film thickness becomes 50% of the maximum film thickness. Compare the sensitivity of sample 1.

For the above samples 2 to 8, use the same method as above for sensitivity evaluation. The results are shown in Table 2.

【Table 2】

By comparing Example 1 and Example 2, all polymers have extremely high sensitivity, but when compound A4 is used, the acid generation efficiency is higher than that of compound A1, thereby improving the reaction efficiency of compound B1. It can be seen that the sensitivity is much higher than that of polymer 1 containing compound A1.

From the results of Example 3, it can be seen that high sensitivity is also obtained when compound A4 and compound A5 serving as a photolytic base are simultaneously included. Compared with Comparative Example 1, when a dimethyl acetal structure is used instead of the hydroxyl group, the reaction caused by the acid generated by Compound A4 is different, so the sensitivity is lower than that of Example 3.

Compared to Example 7, Example 4 is a highly sensitive one. Since the compound E1 contains tin atoms having a high EUV absorption coefficient, the generation efficiency of secondary electrons is improved, so the sensitivity is higher than that of Example 7.

Example 5 is more sensitive than Example 2. The inclusion of Compound D increases the acid-generating efficiency of Compound A4. Therefore, it is thought that the reaction efficiency of Compound B1 is improved and the sensitivity is improved.

It can be seen from the results of Example 6 that the sensitivity is higher than that of Example 7 because the secondary electron generation efficiency is improved by including the compound F1 containing a fluorine atom with a high EUV absorption coefficient.

<Evaluation of electron beam sensitivity: Examples 8 to 10 and Comparative Example 2>

Sample 9 of the above resist composition was spin-coated on a silicon wafer. Sample 9 was prebaked on a hot plate at 110° C. for 1 minute to obtain a substrate on which a coating film with a thickness of 30 nm was formed. On the coating film of this substrate, an electron beam drawing device (ELS-F100T, manufactured by Nippon Elionix Co., Ltd.) was used to draw a 25 nm half pitch (HP) pattern with an electron beam of 125 keV. A developer for patterning was prepared by increasing the acetonitrile concentration by 5% by mass relative to the above developer in which the acetonitrile concentration was optimized for each polymer. The substrate after electron beam irradiation was developed using this developer for 1 minute. It was then rinsed with pure water to obtain a 25nm line and space pattern. The sensitivity of electron beam irradiation was calculated using the irradiation dose at this time as Emax [μC/cm ² ].

For the above-mentioned samples 10~12, the sensitivity evaluation was performed using the same method as above. The results are shown in Table 3. When the minimum concentration of acetonitrile aqueous solution for dissolving the unexposed portion of each polymer was checked in advance, the polymer 2 was 25 mass%, the polymer 4 was 30 mass%, and the polymer 5 was 20 mass%.

【table 3】

From the results of Examples 8 to 10, it can be seen that all polymers can be ^patterned with 25 nm HP at 130 to 160 μC/cm. When converted to an electron beam of 50keV, the sensitivity is 100μC/cm ² , which is very high sensitivity. Since Compound A5 and Compound E1 have acid-deactivating properties, any polymer can be finely patterned without adding an acid diffusion control agent.

The patterned SEM images obtained in Examples 8 to 10 are shown in Figure 1 .

In Comparative Example 2, when a developer for patterning was used, a pattern could not be obtained even with irradiation of 500 μC/ ^cm . This is because the polymer produced from unit A cannot be used in the reaction because comparative polymer 2 does not contain unit B, so that sufficient cross-linking density cannot be obtained, and the developer cannot be fully dissolved in the high-solubility developer.

<Effect of developer on electron beam patterning: Example 11 and Comparative Example 3>

Sample 9 of the above resist composition was spin-coated on a silicon wafer. This sample 9 was prebaked on a hot plate at 110° C. for 1 minute to obtain a substrate on which a coating film with a thickness of 30 nm was formed. An electron beam drawing device (ELS-F100T, manufactured by Nippon Elionix Co., Ltd.) was used to draw a 1:3 pattern of 40 nm lines on the coating film of the substrate with an electron beam of 125 keV. The substrate after irradiation with the electron beam was developed for 1 minute using a developer in which the acetonitrile concentration was optimized for each polymer and a developer for patterning in which the acetonitrile concentration was increased by 5% by mass relative to the developer. Rinse with pure water to obtain a 40nm pattern. At this time, the irradiation dose when developing using the optimized developer is defined as Emax A [μC/cm ² ], and the irradiation dose when developing using a patterning developer that is 5 mass% higher than the optimized concentration is defined as Emax B[μC/cm ² ], find the sensitivity to electron beam irradiation.

For the above-mentioned sample 12, sensitivity evaluation was performed using the same method as above. The results are shown in Table 4. By checking the polymer 2 and comparing the developer concentrations of the polymer 2, when the minimum concentration acetonitrile aqueous solution that dissolved the unexposed portion of each polymer was checked in advance, the polymer 2 was 25 mass % and the polymer 2 was 32 mass %.

As shown in Example 11, the pattern of Sample 9 using Polymer 2 can be obtained by irradiating 120 μC/cm ² regardless of the type of developer. However, the line width and LWR of the pattern depend on the concentration of the developer, and the pattern and LWR obtained with the optimized concentration of the developer are larger. This is because the unexposed polymer reacts slightly due to acid diffusion reactions and becomes insoluble in the optimized developer.

As shown by the dissolution threshold (1) in Figure 3, the optimized developer is only slightly affected by the insolubilization effect, whereas the polymer becomes insoluble and therefore greatly affected by the acid diffusion reaction. However, by using The aqueous developer used for development, in which the acetonitrile concentration is increased by 5% by mass, as shown in the dissolution threshold (2) in Figure 3, can increase the dissolution threshold in unexposed areas where insolubilization reactions caused by minor reactions have occurred. Parts of the polymer may also have a tendency to be dissolved. On the other hand, since the onium salt is decomposed in the exposed part to increase the insolubilizing effect on the water-soluble developer, the effect of insolubilizing only the irradiated area is increased, and a line pattern faithful to the drawing conditions can be obtained at low LWR.

The patterned SEM image obtained in Example 11 is shown in Figure 2(A).

As shown in Comparative Example 3, when the optimized developer is used, Sample ¹² using Comparative Polymer 2 can obtain a pattern by irradiation at 200 μC/cm. When using the optimized developer, the sensitivity is lower than in Example 9 using Polymer 2, but the line width and LWR of the pattern are small. It is considered that this is because the polymer in the unexposed portion has not reacted since acid diffusion reaction is not included. However, when a water-soluble developer for patterning in which acetonitrile was increased by 5% by mass was used, the solubility of the polymer increased, so that the comparative polymer 3 containing no unit B could not obtain a sufficient crosslinking density. , therefore, often cannot be fully dissolved in a developer with high solubility.

The patterned SEM image obtained in Comparative Example 3 is shown in Figure 2(B).

In the case of a chemically amplified resist, since sensitivity and chemical gradient depend on the concentration of the acid diffusion control agent, when the concentration of the acid diffusion control agent is low, acid can be generated and diffused in the exposed portion with a smaller exposure amount. However, when the concentration of the acid diffusion control agent is low, it is difficult to suppress the diffusion of acid to the unexposed portion, so the chemical gradient decreases and the LWR increases (Fig. 4). In order to increase the chemical gradient, a high concentration of acid diffusion control agent must be added in advance to control the acid diffusion in the unexposed parts after exposure, so a large amount of exposure is required (Figure 5). Therefore, there is a trade-off between sensitivity and LWR.

By combining an acid-catalyzed reaction with a reaction that directly decomposes by exposure, the dissolution contrast of the exposed part can be improved compared to the case of using only an acid-catalyzed reaction, and the trade-off between sensitivity and LWR can be slowed down to obtain a product with high sensitivity. degree of low LWR mode. In order to reduce the impact of the acid-catalyzed reaction on the pattern, the reaction efficiency in the resist film can be suppressed by utilizing the reaction between two molecules. Therefore, by changing the concentration of the water-soluble organic solvent in the water-soluble developer, there is a tendency that the elution contrast between the exposed portion and the unexposed portion tends to increase.

The concentration of acetonitrile in the water-soluble developer depends on the components of the resist composition, but is preferably 5 to 60 mass %, and more preferably 20 to 40 mass %. Not limited to acetonitrile, when the concentration of the water-soluble organic solvent in the water-soluble developer is 2 to 10 mass % higher than the minimum concentration of the organic solvent that dissolves the unexposed polymer, the pattern forming ability tends to be improved.

<Synthesis of Polymer 12 and Comparative Polymer 3>

(Synthesis Example 54)

The above synthesis example 52 was followed by using the above compound A4 as the constituent unit A, the compound B1 as the constituent unit B, the compound C1 as the constituent unit C, the compound 1 as the constituent unit D, and the α-methylstyrene polymer 12 as the unit I. .

For comparison, styrene was used instead of α-methylstyrene, and Comparative Polymer 3 was synthesized similarly to the above-mentioned Synthesis Example 52.

【Chemical 74】

The polymer having one type of unit I of the present invention is cross-linked at the exposed part to form a polymer network to change the solubility. At the same time, the linear polymer main chain is depolymerized and shortened. It can be expected that the dissolution contrast at the exposed boundary surface is improved and line width roughness (LWR) is reduced.

<Evaluation of electron beam sensitivity: Examples 12~13>

The above-mentioned resist composition sample 13 was spin-coated on a silicon wafer, and pre-baked on a hot plate at 110° C. for 1 minute to obtain a substrate with a coating film having a thickness of 30 nm. An electron beam drawing device (ELS-F100T, manufactured by Nippon Elionix Co., Ltd.) was used to draw a 1:3 pattern of 50 nm on the coating film of the substrate with an electron beam of 125 keV. The substrate after electron beam irradiation was developed with an acetonitrile aqueous solution of the lowest concentration in the unexposed portion of each polymer prepared in advance for 1 minute, and then rinsed with pure water to obtain 50 nm line pattern. The line width roughness of the obtained pattern was measured with a scanning electron microscope (S-5500, manufactured by Hitachi High-Technology Corporation). Sample 14 was measured in the same manner. As a result of the research, both Examples 12 and 13 used a 20 mass% acetonitrile aqueous solution.

From the comparison between Example 12 and Example 13, one version of the polymer of the present invention has a better LWR than a polymer that does not contain unit I, since by containing unit I, depolymerization of the polymer backbone may occur polymerization. This is believed to be the result of reduced line width roughness (LWR) due to increased dissolution contrast at exposed boundary surfaces due to depolymerization.

[Industrial availability]

According to several aspects of the present invention, it is possible to provide a polymer that has a large absorption efficiency of particle beams such as EUV or electromagnetic waves and has excellent sensitivity, resolution, and patterning, and a resist composition containing the polymer. properties, and resist compositions containing the polymers.

Claims (15)

A polymer comprising unit A and unit B. The unit A has an onium salt structure and generates a first free radical by irradiation with a particle beam or electromagnetic wave. The unit B has a structure bonded by an acid-catalyzed reaction, wherein, The polymer includes unit C, the unit C has a free radical generating structure and generates a second free radical by irradiation of a particle beam or electromagnetic wave. The free radical generating structure contains a carbon atom and a multiple bonding of a carbon atom. At least one multiple bonding of a group composed of multiple bonding of carbon atoms and heteroatoms, and the multiple bonding in the free radical generating structure is not a multiple bonding included in benzene aromatics, and relative to the The molar ratio of unit A to said unit C is 0. The polymer according to claim 1, wherein the unit B is a compound represented by the following general formula (I) or (II) at any position of the compound and the Sp group of the following formula (1) bonded unit;

In the general formula (I), R ² and R 3 are each independently selected from any one of the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group, and E is selected from a direct bond; an oxygen atom; Sulfur atom; and any one of the group consisting of methylene groups, n ¹ is an integer of 0 or 1, n ⁴ and n ⁵ are integers of 1 to 2 respectively, n ⁴ + n ⁵ is 2 to 4, n ⁴ is When 1, n ² is an integer from 0 to 4, when n ⁴ is 2, n ² is an integer from 0 to 6, when n ⁵ is 1, n ³ is an integer from 0 to 4, when n ⁵ is 2, n ³ is 0 to 6. is an integer, when n ² is 2 or more and R ² is an electron donating group or an electron withdrawing group, the two R ² can be selected from oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and Any one of the groups of methylene groups forms a ring structure with each other. When n ³ is 2 or more and R ³ is an electron donating group or an electron withdrawing group, the two R ³ can be selected from oxygen directly or through a single bond. Any one of the group consisting of atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups forms a ring structure with each other; in the general formula (II), R ⁴ is each independently selected from a hydrogen atom; an electron-donating group ; and any one of the group consisting of electron-withdrawing groups, at least one of R ⁴ is the electron donating group, and R ⁵ is selected from a hydrogen atom; an alkyl group that may have a substituent; and an alkyl group that may have a substituent. Any one of the groups consisting of alkenyl groups, at least one methylene group in R ⁵ can be substituted by a divalent heteroatom-containing group, n ⁶ is an integer from 0 to 7, n ⁷ is 1 or 2, and n ⁷ is 1 n ⁶ is an integer from 0 to 5. When n ⁷ is 2, n ⁶ is an integer from 0 to 7. When n ⁶ is 2 or more and R ⁴ is an electron donating group or an electron withdrawing group, the two R ⁴ can be composed of a single The bonds form a ring structure with each other directly or through any one selected from the group consisting of oxygen atoms, sulfur atoms, divalent nitrogen atom-containing groups and methylene groups;

(In the formula (1), L is selected from carbonyloxy, carbonylamino, phenylenediyl, naphthalenediyl, phenylenedioxy, naphthalenedioxy, phenylenedicarbonyloxy, naphthalenedicarbonyl Any one of the group consisting of oxygen group, phenylenedioxycarbonyl group and naphthalenedioxycarbonyl group, Sp is a linear, branched or cyclic alkylene with 1 to 6 carbon atoms that may have direct bonding; substituent group; and any of linear, branched or cyclic alkenylene groups with 1 to 6 carbon atoms that may have substituents, at least one methylene group in Sp may be substituted by a divalent heteroatom-containing group, R ¹ is selected from the group consisting of a hydrogen atom; a linear, branched or cyclic alkyl group with 1 to 6 carbon atoms; and a linear, branched or cyclic alkenyl group with 1 to 6 carbon atoms. In any one of the alkyl groups and alkenyl groups in R ¹ , at least one hydrogen atom in the alkyl group and alkenyl group may be substituted by a substituent, and * represents the bonding site with the compound represented by the general formula (I) or (II). The polymer according to claim 1, wherein the unit A is represented by the following formula (III); [Chemical 4]

In the general formula (III), R ¹ , L and Sp are respectively selected from the same options as R ¹ , L and Sp of the general formula (1), M ⁺ is a sulfonium ion or an iodide ion, and X ^- It is a monovalent anion. The polymer according to claim 3, wherein the unit A is represented by the following formula (IV);

In the general formula (IV), R ¹ , L, Sp and X ^- are respectively selected from the same options as R ¹ , L, Sp and X ^- of the general formula (I), and R ^6a is selected from A straight-chain, branched or cyclic alkylene group with 1 to 6 carbon atoms having a substituent; a straight-chain, branched or cyclic alkylene group with 1 to 6 carbon atoms that may have a substituent; may An arylene group having 6 to 14 carbon atoms having a substituent; a heteroarylene group having 4 to 12 carbon atoms that may have a substituent; and any one of the group consisting of direct bonding, in R ^6a At least one methylene group may be substituted by a divalent heteroatom-containing group, and R ^6b is each independently selected from a straight-chain, branched or cyclic alkyl group with 1 to 6 carbon atoms that may have a substituent; it may have a substituent. A straight-chain, branched or cyclic alkenyl group with 1 to 6 carbon atoms; an aryl group with 6 to 14 carbon atoms that may have a substituent; and a heterocyclic group with 4 to 12 carbon atoms that may have a substituent. Any one of the group consisting of aryl groups, at least one methylene group in R ^6b can be substituted by a divalent heteroatom-containing group, R ^6a and 2 of the 2 R ^6b can be selected from directly or separated by a single bond. Any one of the group consisting of an oxygen atom, a sulfur atom, a divalent nitrogen atom-containing group, and a methylene group forms a ring structure with these bonded sulfur atoms. The polymer according to claim 1, further comprising unit D having an aryloxy group. The polymer according to claim 1, further comprising an organometallic compound-containing unit E having a metal atom selected from the group consisting of Sn, Sb, Ge, Bi and Te. The polymer according to claim 1, further having a unit F represented by the following formula (VIII), the unit F having a halogen atom,

(In the general formula (VIII), R ¹ , L and Sp are respectively selected from the same options as R ¹ , L and Sp of the general formula (I), R ^h is a straight chain which may have a substituent, Branched or cyclic alkyl group with 1 to 12 carbon atoms; linear, branched or cyclic alkyleneoxy group with 1 to 12 carbon atoms that may have substituents; straight chain that may have substituents , branched or cyclic alkenyl group with 1 to 12 carbon atoms; linear, branched or cyclic alkenyleneoxy group with 1 to 12 carbon atoms that may have substituents; carbon atoms that may have substituents Any one of the group consisting of an aryl group with 6 to 14 carbon atoms; and a heteroaryl group with 4 to 12 carbon atoms that may have a substituent, and part or all of the hydrogen atoms substituted by carbon atoms are composed of fluorine atoms or iodine atoms atomic substitution). The polymer according to claim 3, ^wherein Aryl carboxylate anion, tetrafluoroborate anion, hexafluorophosphonate anion, dialkyl sulfonimide anion, trialkyl methyl sulfonate anion, tetraphenyl borate anion, hexafluoroantimonate Any one of the group consisting of monovalent metal onium anions and hydrogen acid anions including this, at least one of the hydrogen atoms of the alkyl group and aryl group in ^X- may be replaced by a fluorine atom. A resist composition containing the polymer described in any one of claims 1 to 8. The resist composition according to claim 9, further comprising any one of an organic metal compound and an organic metal mixture, and the metal is selected from the group consisting of Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At least one of the group consisting of At, Rn and Ra. A method of manufacturing a component, comprising the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition according to claim 9 or 10; and exposing the resist using a particle beam or an electromagnetic beam a photolithography step of the film; and a patterning step of developing the exposed resist film to obtain a photolithography resist pattern. The manufacturing method of a component according to claim 11, wherein the development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent. The method of manufacturing a component according to claim 11, wherein the particle beam is an electron beam and the electromagnetic wave is extreme ultraviolet light. A pattern forming method, which includes the following steps: a resist film forming step of forming a resist film on a substrate using the resist composition according to claim 9 or 10; and exposing the resist film using a particle beam or an electromagnetic beam The photolithography step; the pattern forming step of developing the exposed resist film to obtain a photolithography resist pattern. The pattern forming method according to claim 14, wherein the development in the pattern forming step is performed using an aqueous solution containing a water-soluble organic solvent.